TWI280237B - Process for producing carbonic ester - Google Patents

Abstract

This invention relates to a process for carbonic ester production, characterized by: (1) reacting carbon dioxide with an organometallic-compound mixture comprising a reactive organometallic compound having at least two metal-oxygen-carbon bonds per molecule and a non-reactive compound which is derived from the reactive organometallic compound and is unable to be regenerated to thereby obtain a reaction mixture comprising a carbonic ester formed by the reaction, the non-reactive compound unable to be regenerated, and a modified organometallic compound derived from the reactive organometallic compound and capable of being regenerated; (2) separating the reaction mixture into a first part comprising the carbonic ester and the non-reactive compound unable to be regenerated and a second part comprising the modified organometallic compound capable of being regenerated; and (3) reacting the second part of the reaction mixture with an alcohol to form water and an organometallic-compound mixture comprising a reactive organometallic compound having at least two metal-oxygen-carbon bonds per molecule and a non-reactive compound which is derived from the reactive organometallic compound and is unable to be regenerated, and removing the water from the organometallic-compound mixture.

Description

1280237 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a carbonated vinegar using an organometallic compound and carbon dioxide. More specifically, the present invention is a method for producing a monocarbonate comprising: (1) a reactive organometallic compound having at least two metal-oxygen-carbon bonds in a molecule, and a reactive organometallic compound produced therefrom The organometallic compound mixture formed by the non-reactive non-reactive compound is reacted with carbon dioxide to produce a carbonate-containing ester formed by the reaction, and the non-reactive non-reactive compound is produced from the reactive organometallic compound. a reaction mixture of the regenerable modified organometallic compound, (2) separating the reaction mixture from the first portion containing the carbonate and the non-regeneizable non-reactive compound, and containing the regenerable modified organic a second portion of the metal compound, followed by (3) reacting the second portion of the reaction mixture with the alcohol to form a reactive organometallic compound having at least two metal oxygen-carbon bonds in the molecule The organometallic compound mixture formed by the non-reactive non-reactive compound produced by the reactive organometallic compound and water, and thereafter A method of removing water from the mixture of the organic metal compound. According to the method of the present invention, a carbonate can be produced in a high yield by reacting a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule with carbon dioxide. Carbon dioxide is a non-toxic or uranium-free and inexpensive material. Moreover, in the method of the present invention, the non-reactive non-reactive property can be produced, except that the organometallic compound can be regenerated and recycled. The organometallic compound is excluded from the reaction system, so productivity can be achieved efficiently and stably - 4 - 1280237 (2). Further, since the waste does not require the use of a large amount of a dehydrating agent, the manufacturing method of the present invention is extremely suitable for industrial use and has a high commercial price. [Prior Art] Carbonic acid esters can be used as synthetic gasoline or urethane, pharmaceuticals, pesticides, etc., in addition to additives such as gasoline additives for improving octane oxime and diesel fuel additives for reducing particles in exhaust gas. The alkylating agent, the carbonylating agent, the solvent, and the like used in the case, or the use as a raw material for the electrolyte of the lithium battery, the raw material of the lubricating oil, and the oxidation preventing agent for the anti-rust of the boiler piping, etc., are extremely useful compounds. In the conventional method for producing a carbonate, for example, a method in which phosgene is reacted with an alcohol of a carbonyl source is used. In this method, due to the extremely harmful and extremely corrosive phosgene, extreme care must be taken in handling such as transportation or storage, and it takes a great deal to maintain and manage the manufacturing equipment and ensure safety. In addition, the by-product hydrochloric acid produced by this method also causes difficulty in waste disposal. Other examples include an oxidative carbonylation method in which an alcohol and oxygen are reacted using a medium such as copper chloride using carbon monoxide as a carbonyl source. However, this method is also used because of the extremely high pressure of carbon monoxide, so it still costs a lot of money to maintain and manage the manufacturing equipment and ensure safety. Further, problems such as oxidation of carbon monoxide to generate side reactions such as carbon dioxide occur. Therefore, it is highly desirable to develop a method for safely and efficiently producing carbonates. When the above-mentioned phosgene or carbon monoxide is used as a raw material, the raw material itself is -5 - 802,037 (3) or a halogen such as chlorine is contained in the catalyst. Therefore, in the obtained carbonate, there is still a trace amount which cannot be removed by a simple purification step. halogen. When used in gasoline additives, light oil additives, electronic materials, etc., there is a concern that halogens may be mixed and cause corrosion. Further, since the halogen content is extremely low, a thorough purification step is required to remove it, and therefore, it is highly desirable to develop a production method which does not contain a halogen regardless of the raw material or the catalyst. At present, a method in which carbon dioxide is reacted with ethylene oxide or the like to synthesize a cyclic carbonate and then reacted with methanol to obtain dimethyl carbonate has reached a practical stage. In this method, since carbon dioxide as a raw material has extremely low toxicity and does not cause corrosive substances such as hydrochloric acid, it is an excellent method. However, ethylene glycol and the like as by-products have not been effectively utilized, and ethylene or propylene oxide, which is a raw material of propylene oxide, is also difficult to transport safely, so there is still a need for ethylene and propylene oxide. The manufacturing steps are adjacent to the device, and need to be limited by the device installation of the carbonate manufacturing step. Further, a method for producing a carbonate and water carbonate by reacting carbon dioxide as a carbonyl source in equilibrium with an alcohol in the presence of a catalyst obtained by a metal-oxygen-carbon bonded organometallic compound is known. . This equilibrium reaction is shown, for example, in the following formula (3). Organometallic compound C02 + 2ROH V =.__ ^ RO(CO)OR 4 H20 ( 3 ) (R is a saturated hydrocarbon group or an unsaturated hydrocarbon group) In this method, the carbon dioxide and the alcohol system of the raw materials used are harmless. Words are the ideal step. The feature of this method is the equilibrium reaction obtained by the simultaneous production of the carbonate of the product with water. Water is also produced by the carbon monoxide oxygen-6-1262837 (4) carbonylation process, but the oxidative carbonylation process is non-equilibrium. The equilibrium reaction using carbon dioxide as a raw material is thermodynamically biased toward the raw material system. Therefore, when a carbonate is to be produced in a high yield, for example, there is a problem that the carbonate of the product and water are excluded from the reaction system. In addition, there is a problem that water decomposes the catalyst to hinder the reaction, and the number of cycles (recycling and reuse) of the catalyst is stopped about 2 to 3 times. In order to solve the problem of removing water, various attempts have been made to add various dehydrating agents or methods of use. For example, when a metal alkoxide is used as a catalyst to react an alcohol with carbon dioxide, a high-priced organic dehydrating agent for a dehydrating agent is required. Dicyclohexylcarbonylimine (DCC) and other methods [Collect. Czech. Chem. Commun. Vol. 60, 687-692 (1 995 )], but this dehydrating agent cannot be regenerated and reused, and a large amount of waste is generated. And other issues. An organic dehydrating agent, for example, a method of producing a carbonate by using a carbonate orthoester or the like (JP-A No. 1 1 - 3 5 52 1) (This publication describes "reacting a carbonate orthoester with carbon dioxide", Or "reaction of acetal with carbon dioxide", but in recent research, the actual reaction path is "the reaction of alcohol with carbon dioxide to produce carbonate and water, and then the reaction of water with carbonate orthoester" Path). In this method, the dehydrating agent uses a high-priced carbonate orthoester, and also produces a by-product of methyl acetate [Chemical Device Vol. 41, No. 2, 52-54 (1999)], which also The same problem. Further, as an organic dehydrating agent, for example, a method of using a large amount of an acetal compound (German Patent No. 43 1 0 09) is used, for example, a metal alkane 1280237 (5) compound or dibutyl tin oxide is used as a catalyst to make an acetal. An example of the reaction with carbon dioxide (JP-A-200, No. 3, 629) (the reaction described in the latter publication), after the recent investigation, it was found that the actual reaction path was "the reaction of alcohol with carbon dioxide to produce carbonate and Water, then react water with acetal"). However, in the above publication, it is not clearly described that an acetal compound is efficiently used, and a method for synthesizing waste is not produced. Further, when a condensed 11 compound is used as a dehydrating agent, a by-product may have a ketone. The problem of large amounts of waste such as aldehydes. In the method of using the above organic dehydrating agent, when the number of cycles of the catalyst is to be effectively increased upward, the organic dehydrating agent is stoichiometrically consumed with the carbonate (as a by-product of water) and carbonate. Therefore, a large amount of organic dehydrating agent is consumed. Therefore, the treatment and regeneration methods for a large amount of the organic dehydrating agent which is modified by the dehydration reaction need to be additionally carried out. • There is still the concern of catalyst passivation whether or not a large amount of dehydrating agent is required. In other words, in the method for producing a conventional carbonate using the equilibrium reaction represented by the above formula (3), since carbon dioxide forms a supercritical state, the solubility in a solvent is generally low, and the catalyst molecules are likely to aggregate. At this time, in particular, when organotin which is easily mass-produced is used as a catalyst, there is often a problem of catalyst passivation due to massification. There is also a method of using a solid as a dehydrating agent (Applied Catalysis Vol. 1 42 5 L1-L3 (1 996 )), but this dehydrating agent is not reused, and there is a problem that a large amount of waste is generated. Further, for example, a reaction liquid obtained by reacting an alcohol (methanol) with carbon dioxide in the presence of a metal oxide (dibutyltin oxide) may be cooled to -8-1280237 (6) but recycled to a solid. In the enthalpy of the dehydration agent, a method of slowly shifting the equilibrium to the carbonate side in the dehydration to obtain a carbonate is disclosed (JP-A-200 1 - 2475 197). This is a method in which a known temperature dependency such as water adsorption performance of a known dehydrating agent (e.g., Molecular Sieves) and a dehydrating agent are combined by a known technique. However, the adsorption characteristics of solid dehydrating agents such as water adsorbed on Μ ο 1 ecu 1 ar S ieves are lowered at high temperatures. Therefore, when used as a solvent, they are contained in a large amount in a low molecular weight alcohol, and a trace amount of water is obtained under equilibrium. The portion is removed by adsorption, but the reaction liquid in an equilibrium state under high temperature and high pressure conditions is cooled and then circulated in a crucible packed with a solid dehydrating agent for dehydration. In order to increase the conversion rate of the raw material alcohol, it is generally necessary to return the cooled dehydration reaction liquid to high temperature and high pressure to carry out the reaction. In addition to the extreme energy consumption, there is also a problem that a large amount of solid dehydrating agent is required. In this method, it is a relatively common method for synthesizing a fatty ester having a large balance coefficient, but for a method for producing a carbonate using carbon dioxide and an alcohol as a raw material, the balance of the reaction tends to be toward the raw material side. As described above, there is a problem that it takes a lot of energy to repeat it. Further, when the dehydrating agent for saturated adsorbed water is repeatedly used, it is generally required to perform calcination for several hundred degrees, which is also difficult to call an industrially advantageous step. Further, this method removes only the moisture in the product under equilibrium, so that the higher the concentration of the carbonate as the raw material alcohol is consumed, the more difficult the reaction is to be subjected to the equilibrium reaction specification. Further, the solubility of dibutyltin oxide as a catalyst is extremely low, and it exists almost in a solid state. Therefore, the reaction liquid cooled to room temperature in the cooling step is in the form of a white slurry, so that in the subsequent dehydration step, problems such as the (7) 1280237 dehydration tower which blocks the dehydrating agent are generated. In general, in the organic synthesis reaction, the dehydration method is widely known as a distillation method, but in the step of synthesizing a carbonate using carbon monoxide and an alcohol, for example, the Asahi Glass Industrial Technology Award Research Report v〇l. In the content of the review in 33,3 1 -4 5 ( 1 97 8 ), there has been no record or report on the content of dehydration by distillation. Further, in the method for separating a carbonate containing a reaction solution of a metal alkoxide obtained by reacting carbon dioxide with an alcohol in the presence of a metal alkoxide catalyst, although an example of separation by distillation is used, a metal alkane is used. When an oxide is used as a catalyst, a reverse reaction occurs at the time of distillation separation, so that the produced carbonate is extremely difficult to be separated by distillation in the reaction liquid [J. Sci. J. No. 10,1 7 8 9 - 1 7 94 ( 1 9 7 5 )], in particular, a method of separating a carbonate having a high boiling point from a reaction liquid containing a metal alkoxide in high yield, and there is no report at present. Moreover, the metal alkoxide used in the method is extremely unstable in the moisture in the air, so care must be taken in the treatment, and the current technology using metal alkoxide as a catalyst is not utilized. In the industrial manufacturing method of carbonate. It is speculated that there is no technology that can regenerate the once-passivated catalyst into a high-priced metal alkoxide. Dibutyltin oxide used in a stable state in water as a catalyst raw material user, for example, an example of the formation of dibutyltin dioxane in a reaction system (Japanese Patent No. 3 1 28 5 76), even if the rest is initially fed The reaction is in a stable state, but once the reaction is started, an unstable dibutyltin alkoxide is formed, so that the above problems are not solved. In order to separate the carbonate, the -10-(8) 1280237 reaction mixture is taken out of the reaction system, which will passivate the unstable dibutylstannane oxide without regeneration. Therefore, the high-priced catalyst after the reaction is only a method of disposal. Further, a metal alkoxide ("for example, a dialkyl tin alkoxide") is, for example, heated to 180 ° C, and is known to cause thermal deterioration of a trialkyl tin alkoxide [Journal of Industrial Chemistry 72, No. 7 No. 1543- 1549 (1969)]. The trialkylstan alkoxide formed by thermal deterioration is known to have extremely low carbonate generating ability [J. Org. Chem., Vol. 64, 45 06-45 0 8 (1 999 )]. The trialkylstannane oxide is extremely unlikely to be regenerated into a more active dialkyltin dioxane (which is practically impossible). Further, when the deteriorated product (non-reactive compound which cannot be regenerated) is produced and reused in the metal alkoxide, the concentration of the active catalyst is lowered to cause a change in the reaction rate or the yield of the carbonate. , but not stable production. In this case, in order to make the reaction rate or the yield constant, a small amount of a new metal alkoxide is generally used, but only when a metal alkoxide is newly added, if the deteriorated substance is continuously placed, an activity is generated. The problem of a large amount of deteriorated substances accumulating in the reaction system. In this regard, the method of reusing metal alkoxides cannot be achieved by the current technology, and after the reaction, the metal alkoxide is only a waste disposal method, and it will cause a very uneconomical manufacturing method. As described above, the current method for producing a carbonate of a metal alkoxide and carbon dioxide and an alcohol is used. Since a high-priced metal alkoxide is often deactivated by hydrolysis or the like, it is easily and efficiently regenerated and reused. Prior to the advent of the process, there was still a small amount of metal alkoxide to be combined with a large amount of organic-11-1280237 (9) dehydrating agent or solid dehydrating agent to produce a carbonate. As mentioned above, there are still many problems to be solved in the carbonate manufacturing technology currently used, so it is still a stage that is not practical. In order to solve the aforementioned problems, the inventors first proposed a new technique in Japanese Patent Publication No. WO03/055840. The new technology relates to an organometallic compound containing a metal-oxygen-carbon bond, which is used as a carbonate precursor in a non-catalytic form, and an addition reaction of the organometallic compound with carbon dioxide, and then A method for producing a carbonate in a reaction path in which the formed adduct is thermally decomposed, and this method confirms that a carbonate can be obtained in a high yield. In this way, the above problems caused by the current technology can be almost solved. However, in this method, there remains a problem that unreacted non-reactive organic metal is accumulated in the reaction system. SUMMARY OF THE INVENTION Based on the above circumstances, the inventors of the present invention have made intensive studies on the above-mentioned technique of WO 03/05 5 840 in order to solve the above problems. As a result, it is surprisingly known that in the method for producing a carbonate, (1) a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule is produced from the reactive organometallic compound. The organometallic compound mixture formed by the non-reactive non-reactive compound is reacted with carbon dioxide to produce a carbonate-containing ester formed by the reaction, and the non-reactive non-reactive compound is produced from the reactive organometallic compound. a reaction mixture of the regenerable modified organometallic compound, (2) separating the reaction mixture from the non-reactive non-reactive compound -12-1280237 (10) part 1 and containing The second part of the renewable modified organometallic compound, followed by (3) reacting the second part of the reaction mixture with the alcohol to form a reactivity of at least two metal-oxygen-carbon bonds in the molecule Organometallic compound and organometallic compound mixture formed by the non-reactive non-reactive compound produced by the reactive organometallic compound and water The present invention can be attained by the method of removing water from the organometallic compound mixture thereafter, and the present invention has been completed. In the first portion of the reaction mixture obtained in the step (2), the carbonate can be simply separated by distillation or the like. The organometallic compound mixture obtained in the step (3) is subjected to the above reaction for forming a carbonate via a recovery method (step ( Ο ) reuse. Based on the foregoing findings, the present invention has been completed. Therefore, the main present invention The purpose is to provide a recycling of the reactive organometallic compound without using a dehydrating agent, and to eliminate the reactive organometallic compound which cannot be regenerated from the reaction system, and to continuously repeat the high yield. The above-described and other objects, various features and various effects of the present invention will be apparent from the following detailed description and claims. Provided is a method for producing a carbonate comprising (1) a reactive organometallic compound having at least two metals, oxygen, and carbon bonds in a molecule, and a derivative of the reactive organometallic compound > 13-1280237 ( 17) A method of accumulating a very small amount of carbonate produced in a reaction liquid in a medium decomposition reaction, etc. However, the present invention The method provides a novel method which is completely different from the method and technical idea of the prior art. The reaction by the method of the present invention is basically the same as the reaction proposed by the inventors in the aforementioned WO 03/055 840. Hereinafter, before the method of the present invention is described, the method proposed in WO 03/055 8 84 0 will be briefly described. The method proposed in the publication No. W00 3/05 5 8 40 will have a metal- The oxygen-carbon-bonded organometallic compound is used in a large amount as a carbonate precursor without being used as a catalyst, and the organometallic compound is subjected to an addition reaction with carbon dioxide to synthesize the inclusion of the formed adduct. a carbonate obtained by thermally decomposing the reaction route (step (1)), and secondly, separating the carbonate in the reaction mixture obtained by the above reaction (step (2)), and reacting the obtained residual liquid with an alcohol to form a metal - an oxygen-carbon bonded organometallic compound and water, and then the water is easily removed by distillation or the like to recover the obtained organometallic compound (step (3)), In order to form a carbonate, the above reaction may be repeatedly recycled and reused. The steps of the method (the reaction in the oxime and the reaction in the step (3) are represented by the following formulas (4) and (5), respectively. 1280237 (18) (4) Organic compound + cg.2 * One of organometallic compounds C02 adduct Thermal decomposition carbonate + other thermal decomposition products (5) 13⁄4 + Alcohol supplementation • Water, as in WO 03/0 5 In the method of No. 5,840, it is disclosed that an organometallic compound having a metal-oxygen-carbon bond is mainly used as a precursor of a carbonate to form a reaction with carbon dioxide, which is thermally decomposed to obtain a carbonate. Further, the carbonate is separated from the reaction mixture, and then the residual liquid (containing a metal-oxygen-carbon bonded organometallic compound and a thermal decomposition product of an addition product of carbon dioxide) is reacted with an alcohol to be regenerated to have a metal-oxygen After the carbon-bonded organometallic compound, it is returned to the method for producing a carbonate having a repeating process in the step of forming a carbonate. In the step (1) of the method of W003/0 5584, since at least one part of the organometallic compound having a metal-oxygen-carbon bond changes to a thermal decomposition product, after the end of the step (1), A reaction liquid containing no metal-oxygen/carbon-bonded organometallic compound used in the step (i) may be produced, or may be changed to a thermal decomposition product or a hydrolyzate after the end of the step (2), so that The reaction liquid of the metal-oxygen-carbon-bonded organometallic compound used in the step (1) is not contained, but the metal-oxygen-carbon bonded organometallic compound can be regenerated (before the end of the step (3) ( Re-synthesis) The above method is different from the prior art-21, 1280237 (19), which is governed by the equilibrium state. The equilibrium reaction shown in step (3) can be effectively divided, so that each reaction can be controlled. It is possible to efficiently produce a carbonate while draining the formed carbonate and water to the reaction system. That is, in the step (1) of the above method, the reaction can be carried out in an almost anhydrous state, and in the step (2), the decomposition of the carbonate and the carbonate can be suppressed by the method of separating the carbonate by the reaction mixture. In the reverse reaction, in the step (3), the organometallic compound having the metal-oxygen-carbon bond is regenerated, and then the organic metal compound is recovered by removing water. Among them, in each step, a known chemical technique such as cooling, heating, stirring, pressurization, pressure reduction, and separation can be suitably used to optimize the operating conditions. The method of the present invention is the result of the study for the purpose of making the above method of W003/0 5 840 more effective. In the method of WO 03/05 5 840, there is a problem that a non-reactive non-reactive organometallic compound (degraded product) is gradually accumulated in the reaction system, and the present invention can easily solve the above problems. The organometallic compound is generally highly susceptible to thermal degradation, and when it is repeatedly used, it forms a mixture of an organometallic compound (a non-reactive organometallic compound which cannot be regenerated, that is, a deteriorated substance) which is extremely active in activity with the active organometallic compound, and the latter will gradually The ratio is increased, and therefore, in order to continuously and stably produce, it is necessary to continuously add an active organometallic compound or a compound using the same as a raw material. A method for producing a carbonate using only carbon dioxide and an alcohol as a raw material is extremely difficult to separate from the deteriorated material. Therefore, although it is described that it can be reused, it has not been possible to remove the deteriorated substance from the reaction system. In addition, at present, a part of the total catalyst after use is removed, and after the amount of passivation is measured, a corresponding catalyst is added to the reaction system - (20) !28〇237 使用 using a general catalyst Production method. However, in this method, in order to remove a part of the catalyst having low activity, it is necessary to simultaneously remove several times to several tens of times of the active catalyst. When the above method is used for the reaction using a high-priced catalyst, the production cost will be greatly increased, so that it is hardly used in the general industrial manufacturing method. Therefore, at the time of repeated use, it is an extremely important condition to select the deteriorated material and remove it. As a result of intensive research, the inventors have found that the deteriorated substance has different physical properties (boiling point, solid liquid state, etc.) or chemistry from the useful organometallic compound (ie, the reactive organometallic compound and the regenerable modified organometallic compound). The nature (hydrolyzability, etc.) allows the present invention to be carried out by repeatedly using an organometallic compound while selectively removing at least a part of the deteriorated substance from the reactive organometallic compound. The method of the present invention is a method for producing a carbonate, which comprises (1) reacting a reactive organometallic compound having at least two metal-oxygen-carbon bonds in a molecule, and producing the reactive organometallic compound. a mixture of organometallic compounds formed by a non-regenerating non-reactive compound having at least three metal-carbon bonds in the molecule reacted with carbon dioxide to produce a carbonate formed by the reaction and non-reactive non-reactive And a reaction mixture of a regenerable modified organometallic compound produced from the reactive organometallic compound, (2) separating the reaction mixture from the first containing the carbonated vinegar and the non-regeneizable non-reactive compound And the second part containing the regenerable modified organometallic compound, and then, -23-1280237 (21) (3) reacts the second part of the reaction mixture with the alcohol of the first to form a molecule a reactive organometallic compound having at least two metal-oxygen-carbon bonds therein and having at least 3 golds in the molecule produced by the reactive organometallic compound A method of removing a mixture of an organometallic compound formed by a carbon-bonded non-reactive non-reactive compound with water, followed by removal of water from the mixture of the organometallic compound. First, the compounds used in the present invention will be explained below.

In the step (1) of the method of the present invention, a reactive organometallic compound having a metal-oxygen-carbon bond is used. The reactive organometallic compound having a metal-oxygen-carbon bond used in the present invention is a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule. The foregoing examples are exemplified by reactive organometallic compounds having at least two alkoxy groups. The reactive organometallic compound used in the step (1), for example, at least one compound selected from the group consisting of the organometallic compound represented by the following formula (1) and the organometallic compound represented by the following formula (2) is good.

(wherein, M1 is a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table other than ruthenium; and R1 and R2 are each independently a linear or branched carbon number of 1 to 12; An alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and -24 (22) 1280237 A linear or branched aralkyl group having from 7 to 20 carbon atoms selected from the group consisting of an alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms; An aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted;

R3 and R4 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, Or an alkyl group selected from the group consisting of an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms. a aralkyl group having a carbon number of 7 to 20; further, a and b are each an integer of 〇 to 2, and a + b = 0 to 2, and c and d are each an integer of 0 to 4, and a + b + c + d= 4) (〇R9)i Rsh (2 )

(OR (wherein M2 and M3 are each independently a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table except R3; R5, R6, R7 and R8 are each independently linear Or a branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted carbon number of 6 The number of carbon atoms of the aryl group of 19 and the alkyl group selected from the group consisting of a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms; An aralkyl group, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms; R9 and R1() are each independently a linear or branched carbon number i to 2 -25 - 1280237 (23) a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched carbon number of 2 to 12 or an unsubstituted or substituted aryl group having 6 to 19 carbons and a straight a chain or branched alkyl group having 1 to 14 carbon atoms and an alkyl group selected from the group consisting of a cycloalkyl group having 5 to 14 carbon atoms; 7 to 20 carbon atoms; , f, g, h are each an integer of 0 to 2, and e + f = 0 to 2, g + h = 0 to 2, and i and j are each an integer of 1 to 3, e + f+i=3, g + h+j = 3 ) ° The periodic table used in the present invention is a periodic table defined by the International Pure and Applied Chemistry Joint Baseless Chemical Nomenclature (1989). The organometallic compound used may be a monomer, an oligomer, a polymer or a combination thereof. M1 of the organometallic compound of the formula (1) and M2 of the organometallic compound of the formula (2) used in the present invention M3 is a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table except for strontium. Among them, titanium, tin and chromium are preferred. Considering the solubility of alcohol or the reaction with alcohol From the viewpoint of the nature, tin is more preferable. Examples of R1 and R2 of the organometallic compound of the formula (1) used in the present invention, and R5, R6, R7 and R8 of the organometallic compound of the formula (2), for example, Methyl, ethyl, propyl, η-butyl (each isomer), butyl (each isomer), pentyl (each isomer), hexyl (each isomer), heptyl (each Isomers), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer) Dodecyl (each isomer), 2-butenyl, cyclobutenyl, cyclobutyl, cyclopentyl, -26-1280237 (24) cyclohexyl, cycloheptyl, cyclopentadienyl, An alkyl group of an aliphatic hydrocarbon group having 1 to 12 carbon atoms such as a cyclohexadienyl group; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group or a phenylethyl group; a carbon number of 6 to 20 such as a phenyl group, a tolyl group or a naphthyl group; The aryl group of 20, or may have an ether bond, and a halogenated hydrocarbon group obtained by replacing all or a part of hydrogen of a hydrocarbon group such as nonafluorobutane or heptafluorobutane (each isomer) with a halogen atom is preferred, but is not limited herein. Preferred are, for example, lower alkyl groups. More preferably, a linear or branched alkyl group having 1 to 4 carbon atoms. A compound having a higher carbon number than the compound shown above can also be used, but it is liable to cause damage to productivity due to poor fluidity. Examples of R3 and R4 of the organometallic compound of the formula (1) and R9 and R]() of the organometallic compound of the formula (2), such as methyl, ethyl 'propyl (isomer), butyl (each isomer), 2-butenyl group, pentyl group (each isomer), hexyl group (each isomer), octyl group (each isomer), thiol group (each isomer), sulfhydryl group (each isomer), undecyl (each isomer), dodecyl (each isomer), cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, An alkyl group having a carbon number of 1 to 12, such as a cyclohexadienyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a methoxyethyl group, or a carbon number of 5 to 12 An alicyclic hydrocarbon group, a benzyl group, a phenylethyl group or the like having 7 to 20 carbon atoms, but is not limited thereto. Preferably, the alkoxy group in the organometallic compound represented by the formula (1) and/or the formula (2) is preferably an organometallic compound of an alkoxy group formed by an alcohol having a boiling point higher than that of water at normal pressure. . When the reactive organometallic compound of the step (3) is regenerated and reused, the most preferable state is that each alkoxy group in the organometallic compound represented by the formula (1) and/or the formula (2) is a formula ( 1) R3, R4 and R9, R]G of formula (2) are each independently η-butyl, iso- -27- (25) 1280237 butyl, linear or branched carbon number 5 to The alkyl group of 12, or the linear or branched carbon number of 4 to 12 alkenyl group. Examples of the reactive organometallic compound represented by the formula (1), such as tetramethoxytin, tetraethoxytin, tetrapropoxytin (each isomer), tetrabutoxytin (each isomer) ), tetrapentyltin (each isomer), tetrahexyltin (each isomer), tetraheptyloxy tin (each isomer), tetradecyl tin oxide (isomer), Di-methoxy-diethoxy tin, tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetra-iso-propoxy titanium, tetra-2-ethyl-1-hexyloxy Base titanium, tetrapentyltin oxide, dimethoxy-diethoxy-tin, diethoxy-dipropoxy-tin (each isomer), dimethoxy-dihexyloxy-tin (isomers), dimethyl-dimethoxy-tin, dimethyl-diethoxy-tin, dimethyl-dipropoxy-tin (each isomer), dimethyl Dibutoxy-tin (each isomer), dimethyl-dipentyloxy-tin (each isomer), dimethyl-dihexyloxy-tin (each isomer), dimethyl -diheptyloxy-tin (each isomer), dimethyl-dioctyloxy-tin (each isomer), dimethyl-dimethoxy-tin (each isomer), Methyl-dimethoxy-tin (each isomer), dibutyl-dimethoxy-tin, dibutyl-diethoxy-tin, dibutyl-dipropoxy-tin (each Isomers), dibutyl-dibutoxy-tin (each isomer), dibutyl-dipentyloxy-tin (each isomer), dibutyl-dihexyloxy-tin ( Each isomer), dibutyl-diheptyloxy-tin (each isomer), dibutyl-dioctyloxy-tin (each isomer), dibutyl-didecyloxy-tin (each isomer), dibutyl-dimethoxy-tin (each isomer), monobutyl-monodecyloxy-tin, monobutyl-biphenylethoxy tin, monophenyl — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — -dibutoxy-tin (each isomer), diphenyl-dipentyloxy-tin (each isomer), diphenyl-dihexyloxy-tin (each isomer), Diphenyl-diheptyloxy-tin (each isomer), diphenyl-dioctyloxy-tin (each isomer), diphenyldimethoxy-tin (each isomer) Diphenyl-dimethoxy-tin (each Structure), diphenyl-dibenzyloxy-tin, diphenyl-biphenylethoxy-tin, dimethoxy-bis-(trifluoro-butyl)-tin, diethoxy- Di-(trifluoro-butyl)-tin, dipropoxy-di-(trifluoro-butyl)-tin (each isomer), dibutoxy-di-di-(difluoro-butyl)- Tin (all isomers) and other hospitals such as tin oxide, hospital oxygen, and hospital oxygen. For the reactive organometallic compound represented by the formula (2), for example, 1,1,3,3-tetramethyl-1,3-dimethoxy-distannoxane, 1,1,3,3-tetramethyl 1,1,3-diethoxy distannoxane, 1,1,3,3-tetramethyl-1,3-dipropoxy-distannoxane (isomers), 1, 1,3,3-tetramethyl-1,3-butoxy-distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dipentyloxy Di-n-stannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dihexyloxydoxantane (each isomer), 1,1,3, 3-tetramethyl-1,3-diheptyloxy-distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dioctyloxy-di-tin Oxystane (each isomer), 1,1,3,3-tetramethyl-1,3-dimethoxyoxydistannoxane (each isomer),: I,1,3,3 — Tetramethyl-1,3-dimethoxy-distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dibenzyloxy-distannoxane, 1,1,3,3—Tetramethyl-1,3—Linked Ethyloxy distannoxane, 1,1 -29- 1280237 (27), 3,3-tetrabutyl-..1,3-dimethoxy distannoxane, 1,1,3 ,3-tetrabutyl-based-1,3-diethoxy-distannoxane, 1,1,3,3-tetrabutyl-1,3-dipropoxy-distannoxane Isomer), 1,1,3,3-tetrabutyl-1,3-dibutoxy distannoxane (each isomer), 1,1,3,3-tetrabutyl-1 , 3-dipentyloxy-distannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dihexyloxy-distannoxane (isomers) 1,1,3,3-tetrabutyl-1,3-diheptyloxy-distannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-di Octyloxy distannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dioxaoxy-distannoxane (each isomer), 1, 1 , 3,3 -tetrabutyl- 1,3 -dimethoxyoxy-distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dibenzyloxy- Distannoxane, 1,1,3,3-tetramethyl-1,3-biphenylethoxy Cyclooxane, 1,1,3,3-tetraphenyl-1,3-dimethoxy-distannoxane, 1,1,3,3-tetraphenyl-1,3-di-ethoxy Di-n-doxane, 1,1,3,3-tetraphenyl- 1,3-dipropoxy- dianoxyne (isomers), I, 1,3,3 -tetraphenyl a 1,3 - dibutoxy dianoxa oxonium (all isomers), 1,1,3,3-tetraphenyl-1,3 -dipentyloxy distannoxane (isomeric 1,1,3,3-tetraphenyl-1,3-dihexyloxy-distannoxane (each isomer), 1,1,3,3-tetraphenyl-1,3-di Hepoxy oxa oxoxide (all isomers), 1,1,3,3 - tetraphenyl-1,3-dioctyloxymonostann (each isomer), 1,1 , 3,3-tetraphenyl-1,3-dimethoxyoxy-distannoxane (each isomer),: 1,1,3,3-tetraphenyl-1,3-dimethoxy Mono-n-doxane (-30- 1280237 (28) isomers), 1,1,3,3-tetraphenyl-i,3-dibenzyloxy-distannoxane, 1,1,3 , 3 - tetraphenyl-anthracene, 3-biphenylethoxy oxalate, 1,1,3,3-tetrakis(trifluorobutyl)-1,3-dimethoxy-distannoxane, 1,1,3,3-tetra(trifluorobutyl)-anthracene, 3 Diethoxy-distannoxane, 1,1,3,3-tetrakis(trifluorobutyl)-indole, 3-dipropoxy-one-oxide (iso isomer), 1,1, 3,3-tetrakis(trifluorobutyl)-1,3-dibutoxy-distannoxane (each isomer), i, i, 3, 3 - tetrakis(pentafluorobutyl)-1 3-dimethoxy distannoxane, 1,1,3,3-tetrakis(pentafluorobutyl)-1,3-diethoxy distannoxane, i,1,3,3 — Tetrakis(pentafluorobutyl)-indole, 3-dipropoxy-distannoxane (each isomer), 1,1,3,3 -tetrakis(pentafluorobutyl; ι, 3 - dibutoxy Base-one tin-oxide house (each isomer), 1,1,3,3-tetrakis(pentafluorobutyl)-1,3-dipentyloxy-distannoxane (isomeric), i,i,3,3-tetrakis(heptafluorobutyl)-1,3-dimethoxy-distannoxane, 1,I,3,3-tetrakis(heptafluorobutyl)-1,3 Diethoxy-distannoxane, 1,1,3 ' 3 - four ( Fluorobutyl)-[, 3-dipropoxy-distannoxane (each isomer), 1,1,3,3-tetrakis(heptafluorobutyl)-ι,3-dibutoxy — distannoxane (each isomer) and the like. The above-mentioned reactive organometallic compound may be used singly or in combination of two or more kinds, or may be further added with other organometallic compounds or inorganic metal compounds. The above-mentioned reactive organometallic compound can be used, or azeotrope and a solvent having a carbon number of 4 or more can be azeotroped by a known method (for example, the method described in the Netherlands Patent No. 66 1 242 1). Solution-31 - 1280237 (29) After the reaction, the organometallic compound represented by the formula (1) which is obtained by distillation may be used. In this method, when an organometallic compound having an alkoxy group having 4 or less carbon atoms is described, the method is not applicable, and it is preferably obtained by using dibutyltin dichloride and sodium alkoxide. According to the method described in Japanese Patent No. 2 〇〇丨 1 3 6 6 5 3 7 or Japanese Patent Application No. 200 1 - 3 965 45, the formula (1) synthesized from a metal oxide and an alcohol can be used. An organometallic compound or an organometallic compound represented by the formula (2). According to this method, an organometallic compound having a carbon number of 3 or less, such as a methoxy group, can be obtained. For example, when an organometallic compound having a methoxy group is obtained, it can also be obtained by using dibutyltin with methanol and hexane. At this time, it is surprising that although methanol-hexane is known to have the lowest azeotropy, an organometallic compound can be obtained in an alcohol having a lower boiling point than water while preparing an organometallic compound. The organometallic compound prepared from the alcohol having a lower boiling point than water and dibutyltin oxide is mainly composed of the component represented by the formula (2). When a large amount of the organometallic compound represented by the formula (丨) is to be obtained, it is necessary to The obtained reactant is subjected to distillation to obtain a non-organometallic compound of the formula (1) which is distilled. It can also be obtained by reacting a bismuth chloride with an alkoxide. Hereinafter, in the present specification, the "renewable modified organometallic compound produced from a reactive organometallic compound" related to the above-mentioned reactive organometallic compound and the "non-reactive non-renewable property derived from a reactive organometallic compound" will be described. The terms (organometallic compound) and the like are explained. The reactive organometallic compound used in the present invention is an organometallic compound having at least two metal-oxygen-carbon bonds in the molecule. The renewable modified organometallic compound produced by the reactive organometallic compound-32-1280237 (30) 'mainly refers to a carbon dioxide adduct of the reactive organometallic compound formed by reacting the organometallic compound with carbon dioxide. Further, when the adduct is thermally decomposed, the decomposition product of the adduct formed at the same time as the carbonate is "unable to be structurally specific." Further, the hydrolyzate of the reactive organometallic compound and the hydrolyzate of the carbon dioxide adduct of the reactive organometallic compound are all one of the regenerable organometallic compounds in the present invention. In the present specification, "a non-reactive (organometallic) compound which cannot be regenerated by a reactive organometallic compound" is often referred to simply as "degraded matter". The non-reactive non-reactive (organometallic) compound means that the reactive organometallic compound and/or the carbon dioxide adduct of the reactive organometallic compound is thermally deteriorated, and the activity obtained is remarkably lowered, and the change is not regenerated. For the compound of the organometallic compound. The deteriorated substance (non-reactive compound which cannot be regenerated) is mainly produced by the step (3) of the method of the present invention, and others, for example, may be produced during the production of the reactive organometallic compound. The "degraded product" (non-reactive compound which cannot be regenerated) referred to in the present invention is mainly a compound having at least three metal-carbon bonds per one metal atom in the molecule. Examples of the above compound are compounds represented by the following formula (6) and the like. R11k | 12|R——M—〇R14n ( 6 )

I r13 M m (wherein M is a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table other than lanthanum; -33-1280237 (31) R11 'R1 2, R13 are independent a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or unsubstituted or substituted The number of carbon atoms of the aryl group having 6 to 19 carbon atoms and the alkyl group selected from the group consisting of a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms 7 to 20 aralkyl groups, or unsubstituted or substituted aryl groups having 6 to 20 carbon atoms; R 14 is a linear or branched alkyl group having 1 to 12 carbon atoms and a cycloalkane having 5 to 12 carbon atoms a base, a linear or branched alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms An aralkyl group having 7 to 20 carbon atoms formed by an alkyl group selected from the group consisting of a cycloalkyl group having 5 to 14 carbon atoms; further, k, 1, m are each an integer of 〇 to 2, and k + l + m = 3 or 4, η is an integer of 〇 or 1, and k + l + m + n = 4) the aforementioned compound such as tetraalkyl tin Trialkyltin alkoxides and the like. Further, for example, an oxidized metal or the like of the deteriorated substance (non-reactive compound) contained therein. The foregoing examples include compounds such as Sn02, TiO2, and Zr02. The compound (degraded product) having at least three metal-carbon bonds per one metal atom in the molecule has an organic metal ft compound useful in the present invention (the reactive organometallic compound can be regenerated and modified organic) Metal compounds) different physical and chemical properties. The main feature is that the degraded product has a lower boiling point than the organometallic compound and a lower hydrolyzability than the organometallic compound. Hereinafter, the alcohol used in the present invention of the present invention will be explained. In the method of the present invention, in addition to the use of the first alcohol in the step (3), the second alcohol may be used in the step -34-1280237 (32) (1) as necessary, or, if necessary, Step (2) uses the third alcohol. The first alcohol, the second alcohol, and the third alcohol may be the same alcohol or different alcohols. Examples of the aforementioned alcohols include, for example, an alkyl alcohol having a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkanol having a cycloalkyl group having 5 to 12 carbon atoms, and a linear or branched chain. An enol having an alkenyl group having 2 to 12 carbon atoms, and an alkyl group having 6 to 19 carbon atoms which are unsubstituted or substituted, and a linear or branched alkyl group having 1 to 14 carbon atoms and carbon number An aralkyl alcohol having from 7 to 20 carbon atoms of the alkyl group selected from the group consisting of 5 to 14 cycloalkyl groups. Specific examples of the aforementioned alcohol include methanol, ethanol, propanol, 2-propanol, 1-butanol, 2-butanol (each isomer), 2-methyl-1-propanol, 2-methyl-2. -propanol, cyclobutanol, 1-pentanol, 2-pentanol (each isomer), 3-pentanol, 3-methyl-1-butanol '2-methyl-i-butanol, 2 —Methyl 2-butanol (each isomer), 3-methyl-2-butanol (each isomer), cyclopentanol, 2-methyl-1-cyclobutanol (isomers) , 3-methyl-1-cyclobutanol (each isomer), 1-methyl-1-cyclobutanol (each isomer), cyclobutylmethanol (each isomer), 1-hexanol, 2 — Hexanol (each isomer), 3-hexanol (each isomer), 4-methyl-1-pentanol (each isomer), 3-methyl-1-pentanol (each isomer) ), 2-methyl-1-pentanol (each isomer), 2-ethyl-1-butanol, 3-methyl-2-pentanol (each isomer), 3-methyl-3 - pentanol (each isomer), cyclohexanol, 1-methyl mono; [monocyclopentanol (each isomer), 2-methyl- 1 Monocyclopentanol (each isomer), cyclobutylmethanol (each isomer), 2-cyclobutylethanol (each isomer), 1-cyclobutylethanol (each isomer), (1 A -Phenylcyclobutyl) -35- 1280237 (33) Monomethanol (each isomer), (2-methyl-cyclobutyl)-methanol (each isomer), heptanol (isomers), ring Hexylmethanol (each isomer), (methyl-cyclohexyl)methanol (each isomer), cyclohexylethanol (each isomer), (ethyl-cyclobutyl)-methanol (each isomer), (Methyl-cyclopropyl)ethanol (each isomer), (ethyl-cyclopropyl)methanol (each isomer), octanol (each isomer), decyl alcohol (each isomer), hydrazine Alcohol (each isomer), undecyl alcohol (each isomer), dodecyl alcohol (each isomer), propylene alcohol, butenol (each isomer), pentenol (each isomer) Carbon 1 to 1 such as cyclopentenol (each isomer), cyclopentadienol (each isomer), hexyl alcohol (each isomer), cyclohexenol (each isomer), and the like 2 aliphatic alcohol or alicyclic ring with a carbon number of 5 to 12 Alcohol, benzyl alcohol, phenylethyl alcohol, 1,3-propanediol, 1,2-propylene glycol, cyclohexanediol, cyclopentanediol, etc., aliphatic aliphatic polyols having a carbon number of 1 to 12 or carbon number 5 to 12 An alicyclic polyol or the like, and an aralkyl alcohol such as benzenedimethanol. Among the above alcohols, for example, methanol, ethanol, propanol, 2-propanol, 1-butanol, 2-butanol (each isomer), 2-methyl-1-propanol, 2-methyl- 2 - Propanol, cyclobutanol, 1-pentanol, 2-pentanol (isomers), 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2 Methyl-2-butanol (each isomer), 3-methyl-2-butanol (each isomer), cyclopentanol, 2-methyl-1-cyclobutanol (isomers), 3 monomethyl-1-cyclobutanol (each isomer), 1-methyl-mono; 1-cyclobutanol (each isomer), cyclobutylmethanol (each isomer),: 1-hexanol, 2 —Hexanol (each isomer), 3-hexanol (each isomer), 4 methyl mono-1 pentacene? (each isomer), 3-methyl-1-pentanol (each isomer), -36-1280237 (34) 2-methyl-1-pentanol (each isomer), 2-ethyl 1-1,4-butanol, 3-methyl-2-pentanol (each isomer), 3-methyl-3-pentanol (each isomer '/, cyclohexanol, 1-methyl-1-one ring Pentanol (each isomer), 2-methyl-mono-p-pentanol (each isomer), cyclobutylmethanol (each isomer), 2-cyclobutylethanol (each isomer), 1 1-cyclobutylethanol (each isomer), (1 methyl monocyclobutyl)-methanol (each isomer), (2-methyl-cyclobutyl)-methanol (each isomer), heptanol ( Each isomer), cyclohexylmethanol (each isomer), (methyl-cyclohexyl)methanol (each isomer), cyclohexylethanol (each isomer), (ethyl-cyclobutyl)-methanol ( Each isomer), (methyl-cyclopropyl)ethanol (each isomer), (ethyl-cyclopropyl)methanol (each isomer), octanol (isomer), hexenol, etc. Number 1 to 8 of 1 or 2 grade monohydric alcohol, benzyl alcohol, etc. The number of aralkyl alcohols of 7 or 8 or more is preferably. For example, in the above group, an alkyl alcohol having a boiling point higher than water under normal pressure, a cycloalkyl alcohol, an enol, an alkynol, or the like Specifically, for example, 1-butanol, 2-methyl-1-propanol, a linear or branched alkenyl group having 4 to 12 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms. a cycloalkyl alcohol, and an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms At least one alcohol selected from the group consisting of aralkyl alcohols having 7 to 20 carbon atoms and having an alkyl group selected from the selected alkyl group. The most preferred alcohol is a carbon number of 5 to 8 The following is a description of a method for analyzing a reactive organometallic compound and a deteriorated substance used in the benzene invention - 37 - 1280237 (35) a reactive organometallic compound of the formula (1) and a reactive organometallic of the formula (2) The analysis method of the compound or the deteriorated substance (non-reactive organic metal compound which cannot be regenerated) is, for example, a method using n 9S η - N MR, etc. The method of analyzing the organometallic compound can be, for example, A well-known method (for example, U.S. Patent No. 5,545,600) is used, but the displacement of 11 19Sn-NMR having a structure equivalent to that of the organometallic compound of the formula (1) is susceptible to the organometallic compound of the formula (1) in the sample. The concentration or the presence of alcohol or the like greatly changes, so it is preferable to use Η-NMR, I3C-NMR for the determination. For example, with 2-ethyl-1-hexanol and dibutyltin oxide Examples of the reactive organometallic compound of the formula (1) synthesized are the 119Sn-NMR shift oxime of the corresponding structure as shown in Table 1. Further, the deteriorated substance of the formula (6) (non-reactive non-reactive organic metal) The 119Sn-NMR displacement enthalpy of the equivalent structure is shown in Table 2. The change in the displacement 値 of the deteriorated substance was extremely low, and it was found that the difference was mainly caused by the alkyl group or the alkoxy group, and the signal appeared in the range of 590 to 110 ppm. -38- (36) 1280237 Table 1 Liquid concentration of organometallic compound of formula (1) having 2-ethyl-1-hexyloxy group and 119Sn-NMR shift 値, 1 I9Sn-NMR data wt % δ ppm 48.0 - 64.2 20.5 -19.1 11.2 -6.6 3.4 2.7 Note: The displacement 値(5) corresponds to tetramethyltin (SnMe4). The concentration is the weight concentration (wt%) in heavy chloroform (CDC13). 1280237 (37) Table 2 1] 9Sn — NMR shift 値 1 of the degraded compound of formula (6) with tributyl] 9Sn— NMR data oxime (OR) δ ppm methoxy 109 ethoxy 102 hexyloxy 1 00 Note: Displacement 値 ((5) is corresponding to tetramethyltin (SnMe4). Hereinafter, each step of the method of the present invention will be described in detail. Step (1) of the method of the present invention is to have at least intramolecular a reactive organometallic compound having two metal-oxygen-carbon bonds and an organic non-reactive compound having at least three metal-carbon bonds in the molecule produced by the reactive organometallic compound The metal compound mixture is reacted with carbon dioxide. In the step (1) of the method of the present invention, a carbon dioxide adduct of a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule is first formed, and then the adduct is heated. Decomposition to obtain a carbonate as a main reaction step. That is, the reaction path in the step (1) is an addition bond of carbon dioxide and a reactive organometallic compound to form an adduct, and then the adduct is thermally divided. The step (1) of the method of the present invention is different from the prior art in that an organometallic compound having a metal-oxygen-carbon bond is reacted with a low stoichiometric amount of carbon dioxide. In the current method, for example, a small amount of metal is used. An example of a reaction between a catalyst and high-pressure carbon dioxide in the presence of dibutyltin dimethoxide ( -40 ~ (38) 1280237

Polyhedron, 19, p.  5 7 3 - 5 7 6 ( 2000 )). , using a logarithm of mmol of dibutyltin dimethoxide; the reaction is carried out under the reaction conditions of carbon dioxide. Although the correct number of oxidized carbons is not described, even if the partial pressure of methanol is subtracted, the metal-oxygen-carbon bonded organometallic compound reacts with carbon dioxide at a stoichiometric ratio of 100 times. Under the foregoing conditions, the equilibrium yield can be such that the yield of the carbonate is large relative to the catalyst and the water formed at the same time is produced as free water. Therefore, the hydrolysis of the catalyst catalyst caused by the former often causes great problems, so a dehydration method must be constructed. Among the foregoing conditions, dibutyltin oxide which is a hydrolysis mechanism of the dibutyl group is formed by the reaction in the presence of dibutyltin oxide. Dibutyltin oxide is dissolved in a solvent at room temperature. In the present invention, even when the liquid is cooled to room temperature in the end of step (1), since it is liquid in many cases, the known technology is different in the reaction of carbon dioxide. The reaction state is further in the form of a high concentration of carbon dioxide. Therefore, when the reaction liquid is taken out from the reactor, if the excess is not separated, the carbonate is not separated, so that the carbon dioxide is often separated and returned to normal pressure. The carbon dioxide needs to be repressurized to take advantage of the problem of wasted energy. On the other hand, when carbon dioxide is used, the density of the carbon dioxide gas can be dissolved into a solvent or a catalyst, and the formed carbonate can be dissolved. If it is cooled, a liquid of liquefied carbonic acid is formed. The separation of the produced carbonate from the reaction liquid is also carried out under the condition of 18 MPa at 30 MPa to prepare the above-mentioned chemistry without special amount, but in the reaction system of free water Since the bismuth dimethyl oxide is oxidized, it is recorded that it cannot be dissolved, and the reaction and the above-mentioned large amount of state become a high-pressure carbon dioxide waste, and it is possible to use a uniform layer having a high concentration and a high concentration. The point of view is that the difficult matter -41 - 1280237 (39) steps of the method of the invention (1). In the case where carbon dioxide has a stoichiometric ratio of the reactive organometallic compound in the range of from 1 to 50, more preferably from 1 to 20, and when the amount of carbon dioxide is too large, a high pressure reaction is formed. The use of a reactor configuration with high pressure resistance, in addition, after the end of step (1), a lot of carbon dioxide will be lost when carbon dioxide is to be separated. Therefore, the above stoichiometric ratio is preferably in the range of 1 to 10%. In other words, the amount of the reactive organometallic compound used in the step (1) is preferably in the range of 1/5 〇 to 1 times the stoichiometric amount of the carbon dioxide, and in the range of 1/20 to 1 time. good. In the present invention, the carbon dioxide adduct of the reactive organometallic compound is easily obtained by contacting the reactive organometallic compound with carbon dioxide, and at room temperature (20 ° C), with atmospheric carbon dioxide. When the gas stream is in contact, the carbon dioxide adduct can be generated by heat generation, and a carbon dioxide adduct of 100% can be formed almost. However, as the reaction temperature increases, the yield of the carbon dioxide adduct gradually decreases, and at this time, the contact high pressure carbon dioxide is contacted under high pressure. In the step (1) of contacting with carbon dioxide under high pressure, it is extremely difficult to quantify the yield of the carbon dioxide adduct, so that it is preferably carried out under the pressure required in accordance with the rate of formation of the carbonate, the yield, and the like. This pressure range is generally in the range of atmospheric pressure to 200 MPa. The yield of the carbonate obtained by the reaction in the step (1) is preferably carried out in a stoichiometric ratio of the reactive organometallic compound to 100% or less. More preferably, it is in the range of 50% or less. The reactive organometallic compound used in the method of the present invention has higher hydrolyzability than the obtained carbonate, and generally can be made into 42-!28〇237 (40) to obtain 100% or less of the reactive organometallic compound. Preferably, the carbonate is a stoichiometric ratio of 50% or less, which is such that water produced by hydrolysis of the carbonate does not occur in the reaction liquid. In the prior art, since the reaction is carried out in a stoichiometric ratio of more than 100%, a problem of free water in the reaction system is extremely significant, and it is necessary to add a dehydrating agent having a higher hydrolyzability than the organometallic compound, or an adsorption force. A higher solid dehydrating agent and reacted in its presence. Therefore, it is necessary to use complicated steps or expensive dehydrating agents' and fail to adopt an industrial manufacturing method. In the decomposition reaction of the main reaction in the step (1) of the process of the present invention, the decomposition reaction of the carbonate is obtained by thermally decomposing the carbon dioxide adduct of the reactive organometallic t. The thermal decomposition temperature can be carried out in the range of 20 to 300 °C. In the step (1) of the method of the present invention, the alcohol exchange reaction 'ester exchange reaction and the like can be carried out at the same time as the above decomposition. That is, when the second alcohol is used in the step (1), an alcohol exchange reaction occurs with an oxygen-carbon bond portion of a reactive organic & genus compound having at least two metal-oxygen-carbon bonds in the molecule. A carbonate corresponding to the added alcohol can be obtained. Further, after the carbonate is formed, the second alcohol is further added to carry out a transesterification reaction to form a carbonate corresponding to the second alcohol. Hereinafter, the step (1) will be explained in more detail. Based on the results of the study by the present inventors, step (1) of the method of the present invention produces a carbonate from the reactive organometallic compound and carbon dioxide. Therefore, the second alcohol can be used arbitrarily. However, when the second alcohol is added, the carbonate can be obtained in a high yield, which is preferable. Since there is a reverse reaction of the step (1)S in this case, when the second alcohol is added, a new equilibrium reaction between the thermal decomposition product of the -43-1280237 (41) and the second alcohol other than the carbonate can be generated. There will be cases where the yield of carbonate is increased. When the second alcohol is added to increase the yield of the carbonate, the main component of the reactive organometallic compound can be particularly effective when it is an organometallic compound represented by the formula (2). When the main component of the reactive organometallic compound is a compound represented by the formula (1), since the equilibrium of the thermal decomposition reaction of the step (1) is biased toward the product system, the yield of the carbonate ester is extremely high, so that there is no further improvement. The situation. When the second alcohol contains a large amount of water, the yield of the obtained carbonate is deteriorated, so the water contained in the second alcohol added to the reaction liquid is the amount of the reactive organometallic compound. Preferably, the stoichiometry is 0.  1 or less, more preferably 0. 01 or less. In the step (1), the reaction of the organometallic compound of the formula (1) is carried out by thermally decomposing the addition product of the organometallic compound of the formula (1) and carbon dioxide to form a carbonate, generally from the organometallic of the formula (1). The method of producing a carbonate of a dimer of a compound is well known (ECO INDUSTRY, vol. 6, pll - 18 (200 1 )). In the prior art, dibutyltin oxide is obtained by producing two molecules of carbonate from the dimer. As a result of intensive research, the present inventors have discovered, surprisingly, that when one molecule of the carbonate of the organometallic compound of the formula (1) and the carbon dioxide are decomposed as soon as possible, An organometallic compound mainly of the formula (2) and/or a carbon dioxide adduct thereof can be obtained. At this time, it is not necessary to add alcohol. After the carbonate and the organometallic compound of the formula (2) and/or the carbon dioxide adduct thereof are thus obtained, the step (2) may be carried out immediately, or the organometallic compound of the formula (2) and/or its carbon dioxide may be added. After the product is carbonated, the step (2) may be carried out. The reactive organometallic compound used in the step (1), preferably -44-1280237 (42), is at least selected from the group consisting of the organometallic compound of the formula (1) and the organometallic compound of the formula (2). One type, or at least one part of the organometallic compound used in the step (1) is preferably an organometallic compound of the formula (1). More preferably, the reactive organic metal compound used in the step (1) contains 5 mol% or more when the organometallic compound of the formula (1) is converted into a metal atom. The component to be added in the step (1) may be a solvent. The reactive organometallic compound used in the process of the present invention is in a liquid form in most cases, and may also comprise a partially reactive organometallic compound. Further, when the reactive organometallic compound forms a carbon dioxide adduct in the step (1), a solid form may be formed. When a solid is formed, a carbonate can be formed in the step (1), but the fluidity occupies an important position when the carbonate is continuously produced. Further, in order to increase the reaction speed with carbon dioxide, it is preferable to use a liquid method. In the above case, the step (1) may be carried out after the solvent is added. The solvent to be used may be any alcohol which can correspond to the organic group of the carbonate to be produced, or a tire-inactive solvent. Examples of the inactive solvent include hydrocarbons or ethers. For example, a saturated hydrocarbon having a carbon number of 5 to 20, such as pentane, hexane, cyclohexane, heptane, octane or decane, and a carbon number of 1 to 14 such as benzene, toluene, xylene or ethylbenzene can be used. Saturated alkyl or carbon number 5 to 20. a saturated alkyl ether having 6 to 20 carbon atoms such as an aromatic hydrocarbon, dipropyl ether, dibutyl ether or dihexyl ether; a cyclic alkyl ether having 4 to 20 carbon atoms such as tetrahydrofuran or dioxane; a phenyl group having a carbon number of 0 to a carbon number 8 substituent such as ether, ethyl phenyl ether, cumene ether, benzyl methyl ether or 4-methylanisole, - 45 - 1280237 ' (43) A phenyl ether having 7 to 28 carbon atoms and an alkyl group having 1 to 14 carbon atoms or a cycloalkyl group having 5 to 14 carbon atoms. The reaction temperature of the step (1) is generally in the range of room temperature (20 ° C) to 30 ° C. To quickly terminate the reaction, it is preferably 80 to 200 ° C in 1 〇 minutes. It is carried out within the range of 500 hours. When the reaction of the step (1) is carried out at a high temperature (for example, at 200 ° C or higher), in the 119Sn-NMR analysis, a component formed in the vicinity of 100 ppm from the tetramethyltin standard is often detected, and the component is formed. It is preferred to carry out the reaction in the presence of an additive which is less or inhibited, so that the reaction can be carried out repeatedly. The carbon dioxide and the reactive organometallic compound used in the step (1) may be at a stoichiometric amount at room temperature (20 ° C). When the reaction is carried out at a temperature exceeding room temperature (20 ° C), the reactive organic metal compound is less likely to cause an addition reaction of carbon dioxide, which causes a significant delay in the formation of carbonate. The reaction pressure of the step (1) is generally a normal pressure to 200 MOa, preferably a normal pressure to 100 MPa. If necessary, the carbon dioxide may be simultaneously charged or separated by a part of the reaction. The charge of carbon dioxide can be either intermittent or continuous. In the step (1), it can coexist with other components. Other components which can be effectively used, for example, a component having a function of a dehydrating agent in a reaction system. It is possible to maintain the reactivity of the step (1) in a non-aqueous state as a result of the addition. As the dehydrating agent, for example, a known organic dehydrating agent can be used. As the dehydrating agent, for example, an orthoester such as an acetal compound or trimethyl orthoacetate can be used. For example, an organic dehydrating agent such as dicyclohexylcarbonyldiimine may be used. As the dehydrating agent component, for example, a solid dehydrating agent such as Μ 〇 ] e c U1 a r S i e v e s can be used. When using a solid de-46 - 1280237 (44) aqueous solution, it is preferred to remove the solid dehydrating agent prior to carrying out step (3). In the step (1), the second alcohol can be used arbitrarily. When the second alcohol is used, the amount of the second alcohol in the case of the second alcohol having the same organic group as the alkoxide or aryl oxide of the organometallic compound when the degree of carbonate ester obtained is increased. The amount of the reactive organometallic compound is preferably from 1 time or more to 1,000,000 times the stoichiometric amount, using an alcohol having an organic group different from the reactive organometallic compound, or using only the reaction of the formula (2) In the case of the organometallic compound, the amount of the second alcohol to the reactive organometallic compound is preferably from 2 times to 1000 times the stoichiometric amount, more preferably from 10 times to 1,000 times. When a second alcohol having a mechanical group different from the reactive organometallic compound is used, an asymmetric carbonate can be obtained. Further, as described later, when the second alcohol is used, the yield of the carbonate can be improved, and the effect is much better than the case where only the reactive organic metal compound is used in the formula (2). The reactive organometallic compound is preferably used in the case of using only the formula (2), and the second alcohol can be used in accordance with the desired conditions. After the step (4) described later, when the step (1) is further carried out, the second alcohol may be added to the above range, or the alcohol may be removed if necessary. According to the reaction of the step (1), the carbonate formed by the reaction and the non-reactive non-reactive compound (degraded product) and the regenerable denaturing organometallic compound produced by the reactive organometallic compound may be contained. Reaction mixture. The result of the reaction mixture was analyzed to obtain the desired carbonate, which was the end of step (1). For example, when a carbonate having a stoichiometric ratio of 5% or more to the reactive organometallic compound-47-(45) 1280237 is obtained, the reaction solution may be recovered after returning to normal pressure, or the reaction mixture may be taken from the reactor. It can also be taken out directly. For example, if step (1), step (2), and step (3) are respectively carried out in different reactors, the end liquid of step (3) is injected into the reactor of step (1), and step (1) The reactor is injected into the reactor of the step (2), and the reactor of the step (2) is injected into the reactor of the step (1) or the like to continuously circulate the liquid. The method of circulating the reaction liquid, for example, the step of minimizing carbon dioxide sequestration (1), the amount of carbon dioxide separation in the reactor is a preferred embodiment. After the completion of each step, the reaction solution may be forcibly cooled, or allowed to be naturally cooled, or heated. Further, as will be described later, the step (2) in the carbonate synthesis reaction and the step (2) of the carbonate separation reaction may be simultaneously carried out depending on the case. The step (2) in the method of the present invention comprises the reaction liquid mixture obtained in the step (1), and contains the first part of the carbonate and the deteriorated substance (non-reactive compound which cannot be regenerated), and contains regenerable The modification is a step of separating the second part of the metal compound. In the step (2), the first portion containing the carbonate further contains a deteriorated substance of the organic metal compound to prevent the deteriorated substance from accumulating in the reaction system. Thus, the technical problems that have occurred in the past can be completely solved in the present invention. As described above, when the reaction of the formula (3) is carried out by the current method for producing a carbonate obtained from carbon dioxide and an alcohol, water is also produced at the same time as the production of the carbonate. The current method is to use an adsorbent or a dehydrating agent. It is excluded from the reaction system by contact with water, and the equilibrium reaction is biased toward the product side. This equilibrium state is gradually removed from the reaction system as the carbonate is continuously removed, and the equilibrium is gradually biased toward the production side of the -48 - 1280237 (46) side, which increases the yield of the carbonate. However, the current method for removing carbonates will cause water to accumulate in the reaction solution. As is well known, if water accumulates, the catalyst will lose its catalytic properties due to hydrolysis, and the catalyst after hydrolysis Since the solubility in the solvent is extremely low, problems such as a catalyst blocking the adsorption tower are likely to occur at the time of cyclic dehydration. Further, the catalyst will be passivated by reaction with water, and no method for regenerating it has been found. The reason should be that the carbonate is not effectively separated by the current method. The step (2) of the method of the present invention can be carried out by a known separation method such as a filtration or solvent extraction method generally used or a method of distillation or membrane separation, as long as the effects of the present invention are not impaired. The extraction solvent is preferably a solvent which does not react with a carbonate, for example, a halogenated hydrocarbon such as hexane or cyclohexane, an aromatic such as benzene, toluene or chlorobenzene, or an ether such as an ether or anisole. As the distillation method, for example, a known method can be used. The above method is, for example, a known distillation method under normal pressure, vacuum distillation, pressure distillation, thin film distillation method, or the like. The distillation may be carried out under different conditions from the obtained carbonate, and the temperature may be from 2 ° C to 200 ° C. In this case, other solvents may be added and distilled, or extractive distillation may be carried out. In the case of pressure distillation, as described above, since the reverse reaction occurs and the recovery rate of the carbonate is lowered, when the reaction mixture is subjected to distillation separation of the first portion of the carbonate having a high boiling point, the carbonic acid is removed. When the ester is distilled off from the reaction liquid at a rate which is lost by the reverse reaction, a higher recovery rate of the carbonate can be obtained. Therefore, it is preferable to carry out the adjustment under the moderate adjustment of the temperature or the degree of pressure reduction in accordance with the purpose. In the step (2), the third alcohol may be used as necessary. By adding the third alcohol, the carbonate obtained in the step (1) can be transesterified with the third alcohol * 49 · 1280237 (47) to obtain a carbon number different from the carbonate obtained in the step (1). Carbonate. In addition, the amount of the third alcohol: is generally such that The reactive organometallic compound used in the step (1) is in the range of 10,000 times or less of the same stoichiometric amount. The temperature of the transesterification reaction is usually in the range of room temperature (about 20 ° C) to 200 ° C. In the case of considering the rate of the transesterification reaction or the decomposition reaction of the carbonate at a high temperature, it is more preferably in the range of 50 ° C to 150 ° C. At this time, a catalyst of a known transesterification reaction can be added. The separation of the transesterification from the carbonate can be carried out batchwise or simultaneously. The separation method of the first portion containing the carbonate after the transesterification can be carried out by the above separation method (filtration or solvent extraction, distillation, membrane separation, etc.). According to the method of the present invention, in addition to the symmetric carbonate, a non-symmetric carbonate can also be obtained. At present, a method for producing an asymmetric carbonate by performing a transesterification reaction after producing a symmetrical carbonate has been proposed, but the present invention is a method for directly producing an asymmetric carbonate, so the energy cost is The only preferred manufacturing method for equipment construction. Asymmetric carbonates can be produced in the following manner. Hereinafter, the reactive organometallic compound is exemplified as an alkoxy group-containing organometallic compound. Regardless of the steps. (1) In the step (2), when the alcohol (the second alcohol and the third alcohol) is not used, the two kinds of alkoxy groups different from the reactive organometallic compound used in the step (1) are used. At this time, an asymmetric carbonate can be obtained. The ratio of the two different alcohols used varies depending on the combination of alcohols, and is generally in the range of 2:8 to 8:2. In order to produce a larger proportion of asymmetric carbonates, the closer the ratio of the two different alcohols is, the better. The above preferred range is in the range of 3: 7 to 7 · · 3, more preferably 4 · · 6 to 6 · · 4 - 50 - 1280237 (48). When an asymmetric carbonate is produced using two different alcohols, if an excess amount of, for example, a stoichiometric amount of an alcohol of 10 times or more is used for the reactive organometallic compound, regardless of the alkoxy group of the reactive organometallic compound An asymmetric carbonate having two different alkoxy groups corresponding to the two types of alcohols to which they are added can be obtained. The separation of the first portion containing the asymmetric carbonate can be carried out, for example, by the same method as described above (filtration or solvent extraction, distillation, membrane separation, etc.). There are many cases where a symmetric carbonate is formed simultaneously with an asymmetric carbonate. In this case, the first portion can be separated from the asymmetric carbonate and the symmetric carbonate, and then the symmetric carbonate is blended with the second. The fraction (containing the regenerable modified organometallic compound) is subjected to the step (3), or the symmetrical carbonate is returned to the step (1) or the step (2). In the method of the present invention, as described above, the deteriorated compound carbonate of the reactive organometallic compound is simultaneously separated as the first portion in the step (2). The removal of the deteriorated substance, for example, can remove all the deteriorated substances, or remove a part. It can be changed according to the size of the reactor and the number of times of repeated use. Preferably, for example, more than 1% by weight of the deteriorated substance in the reaction mixture is removed, and more preferably 50% or more is removed. The separation method of step (2) will be described in more detail below. In general, the method of separating the reaction mixture obtained in the step (1) into the first portion and the second portion can be carried out by using the above-mentioned known separation method. Preferably, for example, water is added to separate the phase, a distillation separation method, or the like. It will be explained as follows. (1) Separation method of adding water The water or the aqueous solvent is added to the reaction mixture obtained in the step (!), and mixed into -51 - (49) 1280237, and the mixture is separated into a white paste, and the solid component is separated by filtration. The second portion excluding the regenerable modified organometallic compound is filtered in a solid form, and the carbonate is separated from the first portion containing the deteriorated substance by a filtrate. As the water, any form of water may be used, preferably distilled water and deionized water. In the step (2), the amount of water in the case of adding water is generally in the range of 1 to 1 times the stoichiometric amount of the reactive organometallic compound used in the step (1). The second portion containing the regenerable modified organometallic compound is subjected to phase separation water from the reaction mixture, and is 1 time when the stoichiometric amount of the reactive organometallic compound used in the step (1) is 1 time. Very full. In the step (2), the water temperature in the case of adding water is a temperature at which the added water does not solidify in the reaction mixture, for example, - 20 ° C to 100 ° G, preferably 〇 ° C to l 〇 (The range of TC is more preferably adjusted in the range of 10 ° C to 80 ° C. From the viewpoint of preventing hydrolysis reaction of carbonate, it is preferably from 10 ° C to 50 ° C. Only water can be used. However, when water and a solvent are used, it is preferred to use a solvent which does not cause a reaction of the carbonate. When the second alcohol is used in the step (1), the water can be dissolved in the same alcohol as the second alcohol to be used. When it is used later, the solvent separation step can be made easier. In the step (2), when the third alcohol is added to carry out the transesterification reaction, after the transesterification, the same alcohol as in the reaction liquid is used. After the water is dissolved, it is preferably used by the user. Since the deteriorated material is gradually hydrolyzed and solidified, the time until the filtration is added is performed, and the second portion containing the reformable organometallic compound is solidified and then rapidly Good. During this time, with the reactivity used -52-1280237 (50) organometallic compounds or alcohol The type is different, generally between 30 seconds and 60 minutes after adding water at room temperature. More preferably, it is between 1 minute and 1 minute. (2) Distillation separation method The reaction mixture obtained in step (1), By distillation, the carbonate-containing portion and the first portion of the deteriorated substance are separated from the second portion containing the reformable modified organometallic compound. The carbonate and the deteriorated substance have a boiling point higher than the regenerable change. Since the organometallic compound is low, it is generally known to use a method of separating a distillate type, such as a distillation method of pressurization, depressurization, superheating, thin film distillation, a method of performing distillation using a membrane, etc. Distillation temperature to deteriorate Any temperature at which the vapor pressure is generated is preferably applied between about 20 ° C and 300 ° C. The reaction mixture may contain a carbonate as described above, which is carbonated by a reverse reaction. The amount of ester loss is extremely small, so it is generally preferred to carry out between -20 ° C and 200 ° C. In this case, pressurization or depressurization may be performed to adjust the distillation temperature, or continuous separation or batch separation may be performed. Obtained from step (2) The separation of the carbonate in one part (containing a carbonate and a reactive compound which cannot be regenerated) can be easily carried out by a known separation method (adsorption, distillation, filtration, membrane separation, etc.). Step (3) is synthesis ( Regenerating a step of reacting a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule. The lipid compound in the second portion obtained in the step (2) is, in most cases, a transparent or opaque liquid, for example No solid dibutyltin oxide (which is a solid in the organic solvent at room temperature (about 20 ° C), which is almost insoluble, ～53 - 1280237 (51)), and the second part is not found. Sinochem, the structure of the compound is also not specific. However, surprisingly, according to the invention. In the step (3) of the method, the reactive organometallic compound can be obtained irrespective of the organometallic compound represented by the formula (1) and/or the organometallic compound represented by the formula (2). Step (3), reacting the reaction mixture obtained in the step (2) with the alcohol of the first group to form a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule, and the reactive organic compound A method in which an organometallic compound mixture and water are obtained from a non-reactive compound which cannot be regenerated by a metal compound, and then water is removed from the organometallic compound mixture. If necessary, after the step (3), the organometallic compound obtained in the step (3) may be further recovered and recycled to the step (1) of the step (1) and the alcohol of the first alcohol used in the step (3). The illustration is as shown above. When the above alcohol is used, if necessary, distillation may be carried out for purification, concentration adjustment or the like. From this point of view, a preferred alcohol is an alcohol having a boiling point of 300 ° C or less under normal pressure. The ease of removing the water in the step (3) is preferably carried out using 1-butanol, 2-methyl-1-propanol or an alkyl alcohol having 5 or more carbon atoms, an aralkyl alcohol or the like. The structure of the reactive organometallic compound obtained in the step (3) using the polyol as the first alcohol is not particularly limited, and for example, the organometallic compound of the formula (1) and/or the organometallic compound of the formula (2) Linkages can also be used in the present invention. The amount of the first alcohol used in the step (3), and the amount of the reactive organometallic compound used in the step (1), preferably 1 to 1 Torr using a chemical amount of -54-1280237 (52) The range of 〇〇〇 times is more preferably 2 to l times. The repeated reaction mode is in the case of carrying out the steps (1) to (4), and the second alcohol is also present after the end of the step (2). At this time, an alcohol may be added to make the alcohol of the first step used in the step (3) up to the above range, or may be removed. The moisture removal performed in the step (3) can be carried out by a known method. For example, a method of distilling off or a dehydration column in which a solid dehydrating agent such as Molecular Sieves is used, and a membrane separation method such as pervaporation by membrane separation is preferred. The method of removing moisture from an alcohol is known to be removed by a pervaporation method. And it is most suitable for use in the present invention. When the alcohol has a boiling point higher than the boiling point of water, the heat distillation can easily remove the water. Further, when the alcohol has a boiling point lower than that of water, an azeotropic mixture of alcohol and water can be formed by adding an azeotropic solvent, and the water can be removed by distillation. Namely, it may be removed by using a solid water agent or may be removed by distillation or membrane separation. However, when the organometallic compound mixture is produced in a large amount in a short time, it is preferred to use a distillation method for dehydration. As the distillation method, for example, a known method such as a distillation method under normal pressure, vacuum distillation, pressure distillation, thin film distillation, extraction distillation or the like can be used. The distillation may be carried out at a temperature of from -2 〇 〇c to the boiling point of the first alcohol used in the step (3), preferably from 50 ° C to the boiling point of the first alcohol. At this time, other ingredients can be added. For example, in order to facilitate dehydration, a solvent which can be azeotroped with water or a solvent in which the water of the produced water is equilibrated to increase the hydrophobicity of the reaction liquid can be added. Further, a solvent for adjusting the fluidity of the reaction liquid can be added. The reaction temperature of the step (3) varies depending on the type of the alcohol to be used, and is -55-1280237 (53), and the temperature of the reaction liquid can be in the range of room temperature (about 20 ° C) to 300 t. Implementation. When the dehydration is carried out in the step (3) by distillation, any temperature can be carried out as long as the water can be maintained in the range of the vapor pressure. In order to complete the reaction as quickly as possible under normal pressure, the temperature of the distillate is preferably carried out at a temperature at which a water can be azeotroped with the first alcohol, and in the case where water does not form an azeotrope with the first alcohol. The boiling point of water is preferably carried out. Further, when the reaction is desired to be faster and faster, the reaction may be carried out at a temperature higher than the boiling point of the first alcohol or water by an autoclave or the like, and the water in the gas phase portion may be gradually separated. When the temperature of the reaction liquid is extremely high, the reactive organometallic compound is often deteriorated, and the aqueous liquid may be usually distilled off by a method such as vacuum distillation. When the first alcohol does not form an azeotropic mixture with water, water and an azeotropic solvent may be added, and the water is removed by azeotropic distillation. This method has the advantages of being able to distill off water at a low temperature, so it is preferred. . The solvent is exemplified by saturated or unsaturated hydrocarbons, ethers, halogenated hydrocarbons such as hexane, benzene, toluene, xylene, naphthalene, anisole, 1,4-dioxane, chloroform and the like which can form an azeotrope with water. Wait. From the viewpoint of separating the water by the azeotropic mixture after the azeotropic distillation, it is preferred to use a saturated or unsaturated hydrocarbon having a low solubility in water as a solvent. When the above solvent is used, it is necessary to use an azeotropic method to sufficiently remove the above amount of water. When azeotropic evaporation is carried out using a steaming tower or the like, since the azeotropic mixture can be separated from the distillation column to return the solvent to the reaction liquid, a smaller amount of the solvent can be used, which is a preferred method. The result of the reaction in the step (3) can be, for example, a metal compound having at least one reactivity selected from the group consisting of the formula (1) and/or the formula (2): »56-(54) 1280237 a mixture of organometallic compounds. When the reaction in the step (3) is no longer generating water, the reaction of the step (3) is terminated. Depending on the amount of water removed, it is determined that the yield of the carbonate obtained in the step (1) is repeated, so that it is preferable to remove a large amount of water as much as possible. In general, the amount of water removed in step (3), for example, the range of 0"1 to 1 times the theoretical amount obtained when only the organometallic compound of the formula (1) is formed, is generally 1 times the theoretical amount removed. The following water. According to the study of the present inventors, the amount of water removed in the step (3) during the process of repeating the steps (1) to (4) using the dibutyltin oxide and the alcohol to produce the organometallic compound is The amount of water produced when the organometallic compound is initially produced from dibutyltin oxide and alcohol is small. In the step (2), when water is added to separate the first portion (carbonate-containing and the deteriorated product), since the obtained white solid contains water, the amount of water removed in the step (3) is also exceeded. One-fold the theoretical amount. In the case where the reaction is repeatedly carried out, since the structure of the regenerable modified organometallic compound in the reaction mixture obtained in the step (1) is not specific, it is difficult to obtain the theoretical enthalpy. At this time, it is sufficient to measure the amount of moisture removed over time to minimize the situation in which the water is distilled off. After the end of step (3), excess alcohol can be removed if necessary. When the purity of the carbonate obtained in the step (1) which is repeatedly carried out is considered, it is preferably removed. In the step (1) which is repeated, when the same alcohol as in the step (3) is used, the alcohol may not be removed after the step (3), and the insufficient portion may be added when the step (i) is carried out. -57- 1280237 (55) When the excess amount of alcohol is removed, when the obtained organometallic compound mixture is solid, it can be filtered. . When the mixture of the organometallic compound is liquid, it can be removed by distillation under reduced pressure, or an inert gas such as nitrogen can be blown to remove the alcohol of the vapor pressure portion. At this time, the sufficiently dry inert gas is not used, and the obtained organometallic compound mixture is hydrolyzed with a metal oxide to repeat the reaction, and the yield of the carbonate obtained in the step (1) is extremely low. Step (1) to step (3) may be carried out in stages, or in batch mode. As described above, if necessary, steps (1) and (2) can be performed simultaneously, and if necessary, steps (2) and (3) can be performed simultaneously, and if necessary, simultaneously Step (1) to step (3). Further, when the method of the present invention is repeatedly carried out, if necessary, the step (3) and the step (1) of the subsequent use may be carried out simultaneously. This will be explained below. (When step (1) and step (2) are carried out simultaneously) When the reaction of step (1) is carried out, there are both liquid phase and gas phase portion, and under high temperature and high pressure, carbon dioxide is in a critical state, so that the reaction liquid is uniform. The state or the like, in the case where the steps (1) and (2) are simultaneously performed, 'the liquid phase and the gas phase are separated. The temperature and pressure may vary depending on the type of the alkoxy group of the reactive organometallic compound or the type of the alcohol depending on the type of the alcohol, and may be 200 ° C or less and 8 Μ P a or less. That is, the carbonate has a high solubility in carbon dioxide, so it can be partially dissolved in the gas phase. Therefore, when the step (1) is carried out, the gas phase portion can be reacted under partial separation, so that the first portion (containing a carbonate and a non-regeneizable non-58-2880237 (56) reactive compound) is The reaction mixture was separated. (When step (2) and step (3) are simultaneously carried out) When the reactive organometallic compound is a reactive organometallic compound obtained from an alcohol having a higher boiling point than water, it can be reused for the use of step (1) or step. (2) A case where an alkyl alcohol having 1 to 3 carbon atoms is obtained. The reaction liquid obtained in the step (1) is subjected to an inert gas such as a carbon dioxide gas stream to separate the carbonate and the deteriorated substance from the water under the flow of the inert gas. Further, a known method such as membrane separation can be used, and a method of continuously separating carbonate from water and carbonate and the deteriorated substance from the reaction liquid can be used. (When performing step (1) to step (3) at the same time) When the reaction of step (1) is carried out, there will be a liquid phase and a gas phase portion simultaneously, and the carbon dioxide is in a critical state under high temperature and high pressure, so that the reaction liquid is uniform. In the state of the step (1) to the step (3), the liquid phase and the gas phase are separated. Further, when the reactive organometallic compound is a reactive organometallic compound obtained by using an alcohol having a higher boiling point than water, an alkyl alcohol having 1 to 3 carbon atoms may be reused. More preferably, the alkyl alcohol is methanol, ethanol or the like. Further, the temperature and pressure may vary depending on the type of the alkoxy group of the reactive organometallic compound or the type of the alcohol depending on the type of the alcohol, and is generally 15 (TC or less, 5 MPa or less. Due to water and carbonate The deteriorated substance has a high solubility to carbon dioxide, so it can be partially dissolved in the gas phase. Therefore, when the gas is partially reacted under partial separation -59-1280237 (57), the organic metal can be obtained. The compound is separated from the deteriorated product by regeneration, and in addition to the above method, the reaction of the fixed metal can be carried out by mixing the organometallic compound, and the carbon dioxide and the alcohol having 1 to 3 carbon atoms are passed through the immobilization. The organometallic compound mixture is obtained by simultaneously obtaining water and a carbonate with the degraded product. The carrier for fixing the mixture of the organometallic compound can use a known carrier. (When the method of the present invention is repeatedly carried out, the steps are simultaneously performed ( 3) When the step (1) of the subsequent cycle is performed, when the method of the present invention is repeatedly carried out, when the step (3) is carried out in a carbon dioxide atmosphere or in the presence of carbon dioxide Step (3) and step (i) of the next cycle can be carried out simultaneously, that is, the second part obtained in the step (2) is reacted with an alcohol to regenerate the reactive organometallic compound, which can be produced at the time. The water is removed, and the regenerated reactive organometallic compound is reacted with carbon dioxide to obtain a carbonate. When the step (3) and the subsequent step (1) are simultaneously performed, the liquid phase can be made in the state of the reaction system. Gas phase separation, suitable temperature and pressure, depending on the type of reactive organometallic compound and alkoxy group or the type of alcohol used, generally 200 ° C or less, IMPa. It is used for alcohols having a boiling point higher than 100 ° C under normal pressure, the reaction temperature is below the boiling point, and at normal pressure to 0. The reaction of the reactive organometallic compound with carbon dioxide is carried out at a pressure of 5 MPa or less. More preferably, carbon dioxide is circulated in the reaction liquid of the step (3) under normal pressure, and the produced water and carbon dioxide are simultaneously removed from the reaction system. -60- 1280237 (58) As described above, after the step (3), the reactive organometallic compound mixture obtained in the step (3) may be further recovered, and the cycle is repeated until the step (1) is used. Step (4) is also possible. Thereafter, the steps from the step (1) to the step (4) may be repeated one or more times. The reactive organometallic compound mixture may be cooled during repeated cycles, or may be recirculated after heating. This step (4) can be carried out continuously or in batch mode. In the step (3), when heated at a high temperature or heated for a long period of time, a large amount of deteriorated substances are generated. It is generally preferred to carry out the reaction with a minimum of the composition. The deteriorated substance (non-reactive compound which cannot be regenerated) causes an uneven reaction when the organometallic compound of the above formula (1) and the organometallic compound of the formula (2) are heated, and causes a carbon dioxide gas environment to cause an uneven reaction. This unevenness is delayed, so that the non-reactive compound which cannot be regenerated is mainly generated in the step (3). Step (3) The previously accumulated deterioration product or the newly generated deterioration product generated in the step (3) may be separated by the step (3). It is because the reactive organometallic compound obtained in the step (3) has a lower boiling point than the deteriorated substance represented by the formula (6). In the method of separating the deteriorated substance in the step (3), for example, a known method such as distillation or membrane separation can be used, and for example, a distillation method using pressurization, reduced pressure, or superheat, or a thin film distillation, a method using a membrane for distillation, or the like can be used. . After the water is removed in the step (3), the number of steps for increasing the degree of pressure reduction to distill off the deteriorated product can be reduced, which is a more preferable method. The distillation temperature may be a temperature in which the deteriorated substance is maintained in the range of the vapor pressure, and is preferably between 20 ° C and 300 ° C. Heating at a high temperature There is a fear of increasing the deterioration of the distillation, so it is 20%. (It is more preferable to carry out 1280237 (59) to 200 ° C. In addition to the non-renewable 'reactive compound' having at least three metal-carbon bonds in the above molecule, a solid deteriorated product may be formed. It is presumed that it is produced by forming a heterogeneous product with a non-regenerating reactive compound having at least three metal-carbon bonds in the molecule, and is mainly composed of an oxidized metal such as titanium oxide or tin oxide. The filtration method is filtered. In the step (1), the step (2) and the step (3) in which no water is added, the reaction liquid is in a uniform liquid, and when the organometallic compound is repeatedly used, In the above step, the solid component is precipitated, and the solid deteriorated product can be removed by filtration. The filtration method can be carried out, for example, by a known method, for example, filtration under normal pressure, vacuum filtration, pressure filtration, centrifugal separation, etc. In the case of moisture, since the useful organometallic compound can be hydrolyzed and solidified, it can be simultaneously with the useful organometallic compound when the hydrolysis reaction is sufficiently suppressed. In addition, the contents of the reactor will be described. The reactor form used in the step (1) and the step (2) and the step (3) is not particularly limited, and a stirring tank method or a multi-stage stirring tank method can be used. The method of multi-stage distillation tower, etc., and the combination thereof, various public methods. The foregoing reactor can be used in batch or continuous mode, and the balance between step (1) and step (3) can be effective. From the viewpoint of biasing the product side, a method using a multi-stage distillation column is preferred, and a continuous method using a multi-stage distillation column is preferred. The theoretical number of stages of the multi-stage distillation column is a distillation column having a plurality of stages of two or more stages, which can be continuously The distillation is not particularly limited. For the above-mentioned multi-stage distillation column, for example, a bell tower, a perforated tray column, a piston tower, a flow tower-62-(60) 1280237, or the like, or a Raschig ring is used. , resin ring, wave earrings, saddle type shovel, saddle type shovel, Dixon sputum, McMahon 塡 海 海 海 海 海 海 海 HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL HEL Unexpected material (product name, Sumitomo Heavy ), such as the filling tower of various fillings, etc., can generally be used for the multi-stage distillation tower. Also, the shed section which has both the shed section and the filling section is used. The embodiment of the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the foregoing examples. (Analytical method) (1) Organometallic compound NMR analyzer: JNM - A400 FTNMR system manufactured by JEOL Ltd., Japan] H-, 13C-, 119Sn-NMR analysis of sample solution: Take a reaction solution ranging from 0.1 to lg, and then add 0. 05g tetramethyltin, about 0. 85 g of sodium bicarbonate was used to prepare a sample solution. (2) Gas chromatographic analysis method for carbonates Device: GC-2010 system manufactured by Shimadzu Corporation, Japan (i) Analysis of sample solution Production Scale. 〇6g reaction solution, dehydrated dimethylformamide or ethylene 1280237 (61) nitrile 2. . 5 ml was added to it. Then add the internal standard diphenyl ether about 〇. 〇6g, to obtain a gas chromatographic analysis sample solution. (ii) Gas chromatographic analysis conditions Column: DB-1 (USA, J&W Scientific) Liquid phase: 1 0 0 % dimethyl polyoxane Column length: 30 m Column inner diameter: 0. 25//m film thickness: 1 μ m

Column temperature: 50 ° C ( l 〇 ° C / min temperature rise) 30 (TC spray temperature: 300 ° C detector temperature: 300 ° C detection method: FID (iii) quantitative analysis of carbonate The standard sample is analyzed to be used as a basis for the calibration curve to perform quantitative analysis on the analysis sample solution. (3) Calculation method of yield of carbonate (dialkyl carbonate) The yield of dialkyl carbonate is the use of step (1) The Moir number of the metal atom contained in the reactive organometallic compound is used as a reference, and the Moir% of the obtained dialkyl carbonate is obtained with respect to the Moir number. Example 1 First, as described below, 2-butylhexyloxy-reactive organometallic compound prepared by dibutyltin oxide and 2-ethyl-1-hexanol. It is equipped with a cooling tube for distillation and a thermometer for measuring internal temperature, True 1280237 (62) The immersion of dibutyltin oxide (manufactured by Aldrich, USA) 249g (1. Omol) in a 4-liter four-necked flask of a controller used to adjust the degree of vacuum (manufactured by Nippon Seisakusho Co., Ltd.) ) with 2-ethyl-1-hexanol (Aldrich, USA) Company, dehydrated grade) 650g (5. 〇mol) and a hot water bath for stirring the rotator used. After replacing the air in the flask with nitrogen, start stirring and heat to 1 72 ° C. The water was separated from 2-ethyl-1-hexanol by a splitter while performing a reaction for about 7 hours. The final degree of pressure was 28 KPa. After the distillate portion almost disappeared, the inside of the flask was returned to normal pressure with nitrogen. Using the above operation, about 13 g of water can be distilled off. 141 g of a viscous liquid is obtained, and the obtained viscous liquid is analyzed by 1H-, 13C-, 9Sn-NMR, and it is confirmed that it contains 1, 1, 3 , 3-tetrabutyl-1,3-di(2-ethylhexyloxy)-di-n-n-n-hexane, dibutyltin bis(2-ethyl-hexyl oxide), tributyltin (2-B) Step (1) - 404 g of the above-obtained liquid was poured into a 500 ml autoclave (manufactured by Toyo, Toyo Kogyo Co., Ltd.) and covered with a lid. After replacing the inside of the autoclave with nitrogen, After the secondary pressure of the high pressure vessel connecting the carbon dioxide of the autoclave with the SUS tube and the control valve is set to 4 MPa, Start the control valve 'to introduce carbon dioxide into the autoclave. After stirring for 1 minute, close the control valve, _ warm the autoclave to 1 20 ° C during stirring. At this time 'adjust the back pressure valve to make the high pressure - the internal pressure of the autoclave It is 4 MPa. In this state, the reaction is carried out for 3 hours. Thereafter, it is cooled to about 30 ° C, and the carbon dioxide is statically shunted back to a normal pressure of 65 - (63) 1280237 by a flow divider. The yield of (2-ethylhexyl) was 25%. The reaction solution was analyzed by 4 -, _] 3C -, 1 19Sn - NMR to confirm that it contains tributyltin (2-ethyl-hexyl oxide) and The carbon dioxide adduct is about G · 1 mol (this is a non-reactive non-reactive compound). (Step 2) About 120 g of the liquid after the completion of the step (1) was fed into a thin film distillation apparatus at 130 ° C and about 65 Pa at 3 g/min using a liquid-feeding pump (LC-10AT, manufactured by Shimadzu Corporation, Japan). In Japan, "E-420" manufactured by Shibata Scientific Co., Ltd. distilled volatile components and cooled and recovered. About 14 g of the volatile component was distilled off. The carbonic acid (2-ethyl-hexyl) in the volatile component is about 50% of the di(2-ethyl-hexyl) carbonate contained in the feed liquid. The volatile component was analyzed by 13C- and 119Sn-NMR analysis to confirm that it contained tributyltin (2-ethylhexyl oxide) about 〇.〇2m〇l. (Step 3) 4 ports of 300 ml, which are equipped with a thermometer for measuring the internal temperature of the distillation tube, a vacuum pump, and a controller for adjusting the degree of vacuum (made by Nippon Seisakusho Co., Ltd.). In the flask, about 100 g of the nonvolatile component obtained in the above step and 5 g of dibutyltin oxide (manufactured by Aldrich Co., Ltd., USA) and 2-ethyl-1-hexanol (manufactured by Aldrich Co., Ltd., USA) were immersed. Grade) 216 § (1.7111111〇1) with a hot water bath for the vortex used for agitation. After replacing the air in the flask with nitrogen, stirring was started and heated to 1 72 °C. The water was separated from 2-ethyl-66-1280237 (64) benzyl-1-hexanol under a slow depressurization using a splitter while reacting for about 7 hours. The final degree of decompression is 28 KPa. After the distillate portion almost disappeared, the inside of the flask was returned to normal pressure with nitrogen. The viscous liquid was obtained, and the viscous liquid prepared was analyzed by H-,]3C-, 119Sn-NMR to confirm that it contained 1,1,3,3-tetrabutyl- 1,3-di-(2-B 1,1-hexyloxy)-di-n-n-n-hexane, dibutyltin bis(2-ethyl-hexyl oxide), tributyltin (2-ethyl-hexyl oxide) (of the aforementioned 3 compounds, the first 2 compounds are Regenerated modified organometallic compounds, the last one being a non-reactive non-reactive compound). The viscous liquid obtained in the step (3) can be recovered, and the step (1) is further carried out. 79 g of the liquid obtained above is poured into a 100 ml autoclave (manufactured by Toyo Kogyo Co., Ltd.), and the lid is placed. After replacing the inside of the autoclave with nitrogen gas, the secondary pressure of the high pressure vessel connected to the carbon dioxide of the autoclave was set to 4 MPa via a SUS pipe and a control valve, and then the control valve was opened to introduce the carbon dioxide into the autoclave. After stirring for 10 minutes, the control valve was closed, and the autoclave was heated to 120 °C with stirring. At this time, the back pressure valve was adjusted so that the internal pressure of the autoclave was 4 MPa. The reaction was carried out for 3 hours in this state, and then cooled to about 30 ° C, and the carbon dioxide was statically shunted back to normal pressure using a flow divider to obtain a transparent reaction liquid. The yield of di(2-ethylhexyl) carbonate is about 25. The liquid after the end of step (1) is about 25 g, and the liquid delivery pump (made by Shimadzu Corporation, LC-10AT) is used at 3 g/ In a minute, a thin film distillation apparatus (1280237 (65) 'E - 42 0, manufactured by Shibata Science Co., Ltd., Japan) of 130 ° C and about 65 Pa was fed to distill off volatile components, and was cooled and recovered. Distill off about 14 g of the volatile component. The carbonic acid (2-ethylhexyl) in the volatile component is about 50% of the carbonic acid (2 · (ethylhexyl)) contained in the feed solution. The volatile component liquid uses 4, 13C, and n9Sn. - NMR analysis confirmed that it contained tributyltin (2-ethylhexyl oxide) about 5 mol. Example 2 First, as shown below, a hexyloxy group was prepared from dibutyltin oxide and hexanol. In an autoclave of 200 ml (manufactured by Toyo Kogyo Co., Ltd.), 24.9 g (100 mmol) of dibutyltin oxide (manufactured by Aldrich Co., Ltd.) and hexanol (manufactured by Aldrich Co., Ltd., USA) were added. Level) 5 l.lg (5 00mmol), cover the lid. After replacing the inside of the autoclave with nitrogen, start stirring and heat to 160 ° C. After about 30 minutes, turn on the autoclave shunt to make high pressure. A small amount of the kettle liquid was poured into the nitrogen gas, and the water and hexanol were distilled off through a splitter for 4 hours. After the distillation component almost disappeared, the autoclave was cooled to about 30 ° C to obtain a viscous reaction mixture. The mixture was analyzed by 1H-, 13C-, 119Sn-NMR to confirm its 1 ,1,3,3—tetrabutyl-1,3-dihexyloxy-di-n-n-n-decane about 40 mm ο 1 '- butyltin-hexyl oxide about 6 mmol, tributyltinhexyl oxide about 4 mmol (Step 1) In a 200 ml autoclave containing 68- 1280237 (66) of the above-obtained organometallic compound having a hexyloxy group, hexanol (manufactured by Aldrich, USA, dehydrated grade) 61.5 g. (602 mmol) was added. The lid is closed on the back. After the pressure of the SUS tube and the control valve to the high pressure vessel connecting the carbon dioxide of the autoclave is set to 5 MPa, the control valve is opened to introduce carbon dioxide into the autoclave. After stirring for 1 minute, The control valve was closed, and the autoclave was heated to 180 ° C with stirring. The pressure at this time was about 7.5 MPa. The reaction was carried out for 6 hours in this state, and then cooled to about 30 ° C, and the carbon dioxide was quietly cooled using a flow divider. The ground stream is returned to normal pressure, and the yield of dihexyl carbonate in the transparent reaction solution is 14% 步骤 (Step 2) After the end of the step (1), 10 g of hexanol containing 1% of water is statically injected into the high pressure. In the kettle, after stirring for about 1 minute, the stirring is stopped. After that, the white slurry was filtered using a membrane filter (manufactured by Pharmacy, manufactured by ADVANTEC Co., Ltd., H020A142C), and the white solid component was washed twice with 20 ml of hexanol, and the obtained filtrate was transferred to an eggplant type flask. The mixture was heated under reduced pressure in a 16 (TC water bath). The hexanol was distilled with tributyltin hexoxide and dihexyl carbonate, and the yield of dihexyl carbonate was 13%. The dibutyltin hexoxide was distilled off to about 2 mmol. A viscous liquid remained on the flask. (Step 3) 'The white solid component obtained in the step (2) and the viscous liquid remaining in the flask after distillation of dihexyl carbonate were placed in an autoclave of 20 ml (曰-69-1280237 (67), Toyo In the high pressure company, hexanol (manufactured by Aldrich, USA), 5 1 .lg (500 mmol) was added and the lid was closed. After the autoclave was replaced with nitrogen, stirring was started and heated to 160 °C. After about 30 minutes, the autoclave splitter was turned on, and a small amount of the autoclave's kettle liquid was poured into the nitrogen gas, and water and hexanol were distilled off through a splitter for 4 hours. After the distillate component almost disappeared, the autoclave was cooled to about 30 °C. Using 1H-, nC-, 119Sn-NMR analysis results, it was confirmed that it contained 1,1,3,3-tetrabutyl-1,3-dihexyloxy-di-n-decane, about 40 mmol, dibutyltin dihexyl. The oxide is about 7 mmol and the tributyltinhexyl oxide is about 4 mmol. After the end of the step (3), the treatment of the step (1) is carried out. In the autoclave after the end of the step (3), 61.5 g (602 mmol) of hexanol (manufactured by Aldrich Co., Ltd., dehydrated grade) was added, and the lid was capped. After the secondary pressure of the high pressure vessel connected to the carbon dioxide of the autoclave was set to 5 MPa through the SUS pipe and the control valve, the control valve was opened to introduce the carbon dioxide into the autoclave. After stirring for 10 minutes, the control valve was closed, and the autoclave was heated to 180 ° C with stirring. The pressure at this time is about 7.5 MPa. The reaction was carried out for 6 hours in this state, and then cooled to about 30 ° C, and the carbon dioxide was statically refluxed to a normal pressure using a flow divider, and the yield of dihexyl carbonate in the transparent reaction liquid was 14%. After the end of the step (1), 1 kg of hexanol in water was poured into the autoclave, and after stirring for about 1 minute, the stirring was stopped. After the autoclave is turned on, it has a white slurry. This white slurry was filtered using a membrane filter (manufactured by ADVANTEC Co., Ltd., H02 0AM2C), and the white solid 1280237 (68) was washed twice with 20 ml of hexanol, and the filtrate was transferred to an eggplant flask at 160°. The C water bath was subjected to heating and vacuum distillation. The hexanol was distilled with tributyltin hexoxide and dihexyl carbonate, and the yield of dihexyl carbonate was 13%. The dibutyltin hexoxide was distilled off to about 2 mmol. Example 3 First, a reactive organometallic compound having a 3-methyl-butoxy group was obtained from dibutyltin oxide and 3-methyl-1-butanol as shown below. In a 4-liter 4-cylinder flask equipped with a vacuum controller and a vacuum pump with a water-distillation receiving tube (Dean-Stark trap), dibutyltin oxide (manufactured by Aldrich, USA) was immersed in 70.5 g (0.28 mol). 502 g (5.7 mol) with 3-methyl-1-butanol (manufactured by Aldrich Co., USA) and a rotator used for stirring. The flask was immersed in an oil bath at 140 ° C, stirring was started, and the pressure was gradually reduced to about 90 KPa. While the distillate was removed in this state, the pressure was gradually reduced to 85 KPa. The reaction lasted for 12 hours. Thereafter, the unreacted materials were slowly depressurized to distill off the unreacted alcohol, and finally the unreacted alcohol was distilled off at a pressure of about 200 Pa for 30 minutes. The flask was taken out of the oil bath and cooled to return nitrogen to normal pressure. 127g of viscous liquid was obtained, and the liquid result of the analysis hall was found to be about 2 600 m ο 1 of water. The obtained viscous liquid was analyzed by 4, 3C-, 119Sn-NMR, and it was confirmed that it contained dibutyl-di(3-methyl-butoxy)-tin, 1, 1, 3, 3 - 4 Butyl-1,3-di-(3-methyl-butoxy)-di-n-n-hexane, tributyl-(3-methyl-butoxy)-tin. -71 - 1280237 (69) Step (1) In a 200 ml autoclave (manufactured by Toyo Kogyo Co., Ltd., Japan), 1 14 g of the above-mentioned viscous liquid was poured, and the lid was placed. After replacing the inside of the autoclave with nitrogen gas, the secondary pressure of the high-pressure vessel connected to the carbon dioxide of the autoclave was set to 5 MPa via a SUS pipe and a control valve, and then the control valve was opened to introduce carbon dioxide into the autoclave. After stirring for 1 minute, the control valve was closed and the autoclave was heated to 120 °C with stirring. At this time, the internal pressure of the autoclave was adjusted to 4 MP a, and the reaction was continued for 4 hours. The mid-sampling results showed that after 1 hour of reaction, 1 8% of bis(3-methyl-butyl)carbonate was formed, and the yield after 2 hours was 20.4%. After the autoclave was allowed to cool, the carbon dioxide was separated. (Step 2) After the end of the step (1), after cooling the autoclave to room temperature (about 20 ° C), the reaction mixture was opened and taken out. Then, it was placed in an eggplant type flask equipped with a cooling tube and a vacuum pump and a vacuum controller (manufactured by Nagano Seisakusho Co., Ltd., Japan), and placed in a stirring rotor. Thereafter, the eggplant flask was immersed in an oil bath and stirring was started. The temperature of the oil bath was 140 ° C, and after decompressing and distilling off 3-methyl-1-butanol, about 9 g of di(3) was obtained after distilling off bis(3-methyl-butyl) carbonate. Methyl monobutyl)carbonate with 1 mmol of tributyl(3-methyl-butoxy)-tin. -72- 1280237 (72) The distillation residue obtained in the step (2) and 3 - methyl-1-butanol (manufactured by Aldrich, USA) 5 02 g (5.7 mol), dibutyltin oxide lg (4 mmol), and Stir the rotator used. The flask was immersed in an oil bath at 140 ° C, stirring was started, and the pressure was gradually reduced to about 90 KPa. While the distillate was removed in this state, the pressure was gradually reduced to 85 KPa. The reaction was continued for 20 hours after the start of the reaction. Thereafter, the unreacted materials were slowly depressurized to distill off the unreacted alcohol, and finally the unreacted alcohol was distilled off at about 200 Pa for 30 minutes. The obtained viscous liquid was sampled and analyzed by 4, 13C-, 119Sn-NMR to confirm the formation of dibutyl-di(3-methyl-butoxy)-tin and 1,1,3,3-tetradecene. The base is 1,3 -di-(3-methyl-butoxy)-di-n-n-n-hexane, followed by the formation of about 2 mmol of tributyl-(3-methyl-butoxy)-tin. This was immersed in an oil bath having an internal liquid temperature of about 93 ° C, and the distillate was distilled off under a reduced pressure of 50 Pa. The flask was taken out of the oil bath and cooled to return nitrogen to normal pressure. A viscous liquid of 1 1 〇g was obtained. The obtained viscous liquid was analyzed by 1H-, 13C-, and 119Sn-NMR to confirm that it contained dibutyl-di(3-methyl-butoxy)-tin and 1,1,3,3-tetrabutyl- 1,3-Di-(3-methyl-butoxy)-di-n-n-hexane, and about 1 mmol of tributyl-(3-methyl-butoxy)-tin was distilled off. Industrial Applicability: According to the method of the present invention, a carbonate can be obtained in a high yield from a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule and carbon dioxide. Carbon dioxide is not toxic or rot-resistant and inexpensive, and -75-(73) 1280237, the method of the present invention can be used to regenerate and recycle the organometallic compound, and can also generate non-reactive non-reactive Since the organometallic compound is excluded from the reaction system, it can be produced stably and efficiently. Further, since the dehydrating agent for the waste is not required to be used in a large amount, the manufacturing method of the present invention is extremely useful in the industry and has a very high commercial price. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1 19 S η NMR chart of a reactive organic compound having a 2-ethylhexyloxy group used in the step (1) of Example 1, and Fig. 2 is a step of Example 1. (2) 19Sn-NMR chart of the non-regenerated which was separated and distilled. ...76 -

Claims (1)

1280237 Picking up, applying for patent scope 1 Patent application No. 9212 1693 Amendment of September 21, 1995, a method for producing a carbonate, characterized in that it comprises (1) a reactive organometallic compound having at least two metals-oxygen-carbon bonds in the molecule, and the reactivity The organometallic compound mixture formed by the non-regenerating non-reactive compound (degraded product) having at least three metal-carbon bonds in the molecule produced by the organometallic compound is reacted with carbon dioxide to obtain a carbonate formed by the reaction. And a non-reactive non-reactive compound and a reaction mixture of a regenerable modified organometallic compound produced from the reactive organometallic compound, (2) separating the reaction mixture from the first portion containing the carbonate and the non-renewable non-reactive compound (degraded product), and containing the second portion of the renewable modified organometallic compound, In the above, the separation is carried out by using at least one separation method selected from the group consisting of distillation, extraction and filtration, and then (3) reacting the second portion of the reaction mixture with the first alcohol. And forming a reactive organometallic compound having at least two metal-oxygen-carbon bonds in the molecule and a non-renewable non-reactive property having at least three metal-carbon bonds in the molecule produced by the reactive organometallic compound A method in which a mixture of an organometallic compound formed by a compound (degraded product) and water is followed by removal of water from the mixture of the organometallic compound. 2. The method of claim 1, wherein after the step 1280237 (3), the organometallic compound mixture obtained in the step (3) is recovered and recycled to the step (4) used in the step (1). 3. The method of claim 1 or 2, wherein the reactive organometallic compound used in the step (i) comprises an organometallic compound represented by the following formula (1) and an organic metal represented by the following formula (2) At least one compound selected from the group of compounds; (〇R4)d R]a—Μ1—(OR3)c (wherein M1 is a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table other than ruthenium; R1 and R2 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a linear or branched alkenyl group having 2 to 12 carbon atoms. An unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms and a ring group having a carbon number of 5 to 14 An alkyl group having 7 to 20 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms; R3 and R4 are each independently a linear or branched carbon number of 1 to 12 a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear chain a aralkyl group having a carbon number of from 7 to 20 which is composed of an alkyl group selected from the group consisting of an alkyl group having 14 carbon atoms and a ring group of 5 to 14 carbon atoms; and, -2 - 1280237 a and b are each an integer from 〇 to 2, and a + b = 0~2, c and d are each an integer from 0 to 4, and a + b + c + d = 4) (〇Λ R8h R5e—Μ2—ο—Μ3-R7g Ri5f (〇R10)i (where, M2 and M3 are each independently a metal atom selected from the group consisting of Group 4 and Group 14 elements of the periodic table except R3; R5, R6, R7 and R8 are each independently a linear or branched carbon. a hospital base of 1 to 12, a ring of 5 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms and an alkyl group having 7 to 20 carbon atoms selected from a group selected from the group consisting of a cycloalkyl group having 5 to 14 carbon atoms, or not Substituted or substituted aryl having 6 to 20 carbon atoms; R9 and R1() are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a linear or branched carbon number of 2 to 12 An alkenyl group, or an unsubstituted or substituted aryl group having 6 to 19 carbon atoms and a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms; The selected alkyl group is composed of an aralkyl group having 7 to 20 carbon atoms; further, e, f, g, and h are each an integer of 0 to 2, and e + f = 〇 〜 2, g + h = 〇 〜 2 , i and j are each an integer of 1 to 3, and e + f + i = 3, g + h + j = 3) ° 4. The method of claim 3, wherein the formula (1) -3 - 1280237 R3 and R4 and R9 and R1() of the formula (2) are each independently η-butyl, iso-butyl, linear or branched alkyl having 5 to 12 carbon atoms, or linear Or a branched carbon number of 4 to 12 alkenyl groups. 5. The method of claim 3, wherein M1 of the formula (1) and M2 and M3 of the formula (2) are tin atoms. 6. The method of claim 3, wherein the reactive organometallic compound used in the step (1) is an organotin oxide and an alcohol. 7. The method of claim 1 or 2, wherein in the step (1), the reactive organometallic compound is selected from the group consisting of monomers, oligomers, polymers, and conjugates. At least one form. 8. The method of claim 1 or 2, wherein the amount of the reactive organometallic compound used in the step (1) is in the range of 1/50 to 1 times the chemical amount of carbon dioxide. 9. The method of claim 1 or 2, wherein the reaction in the step (i) is carried out at 20 ° C or higher. The method of claim 1 or 2, wherein the reaction of the step (1) is carried out in the presence of the same or different second alcohol as the first alcohol used in the step (3). 11. The method of claim 1 or 2, wherein in step (2), the separation of the first part from the second part of the reaction mixture is carried out in the first step of the step (3). The alcohol is the same or different in the presence of the third alcohol. 12. The method of claim 1 or 2, wherein the alcohol used in the step (4-4 - 1280237 3) is a linear or branched carbon number of 1 to 12 Alkyl alcohol, a cycloalkyl alcohol having a carbon number of 5 to 12 cycloalkyl groups, an alkenyl alcohol having a linear or branched carbon number of 2 to 12 alkenyl groups, and an unsubstituted or substituted carbon The number of carbon atoms of the aryl group of 6 to 19 and the alkyl group selected from the group consisting of a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms At least one alcohol selected from the group consisting of 20 aralkyl aralkyl alcohols. 13. The method of claim 12, wherein the first alcohol has a boiling point higher than water at normal pressure. 14. The method of claim 13, wherein the first alcohol is a monobutanol, a 2-methyl-1-propanol, a linear or branched carbon number of 5 to a 1 alkyl alcohol, an alkenyl alcohol having a linear or branched carbon number of 4 to 12 alkenyl groups, a cycloalkyl alcohol having a carbon number of 5 to 12 cycloalkyl groups, and unsubstituted or a substituted alkyl group having 6 to 19 carbon atoms and an alkyl group selected from the group consisting of a linear or branched alkyl group having 1 to 14 carbon atoms and a cycloalkyl group having 5 to 14 carbon atoms At least one alcohol selected from the group consisting of aralkyl alcohols having 7 to 20 aralkyl groups. The method of claim 1 or 2, wherein the method of removing water in the step (3) is carried out by membrane separation. 16. The method of claim 15, wherein the membrane separation is a pervaporation method. The method of claim 1 or 2, wherein the method of removing water in the step (3) It is carried out by distillation.